Chlorination process, alkylation of products of said process and some products thereof

ABSTRACT

Compounds having acidic protons and a molecular structure which can delocalize the electron density of the conjugate base (target compounds) are chlorinated by contacting such compounds with a perchloroalkane and aqueous base in the presence of a phase transfer catalyst which is an tetraalkylammonium hydroxide. Chlorinated products, preferably gem-dichloro compounds, are produced. The gem-dichloro compounds are useful for alkylation of aromatic compounds. For instance fluorene is chlorinated to form 9,9-dichlorofluorene which is reacted with such compounds as phenol or aniline to form such compounds as 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(aminophenyl)fluorene, or 9-aminophenyl-9-chlorofluorene.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional of application Ser. No. 08/090,597 filed Jul. 12,1993 now U.S. Pat. No. 5,387,725 which is a continuation in part of U.S.application Ser. No. 07/789,232 filed Nov. 7, 1991, now abandoned whichis incorporated herein in its entirety.

This invention relates to chlorination, particularly to chlorination oforganic compounds having acidic protons. The invention also relates tosubsequent reaction of certain chlorinated products, more particularlythe use of these products to alkylate aromatic compounds.

Products of compounds such as fluorene in which the acidic protons havebeen replaced by chlorine undergo alkylation reactions which are usefulin preparing other compounds such as bis(hydroxyphenyl)fluorenes andbis(aminophenyl)fluorenes and other functionally substituted aromaticcompounds which in turn find applications as monomers for highperformance polymers. It is particularly important that the chlorinationbe specific to produce the desired isomers, preferably in thesubstantial absence of other chlorination products. For instance, in thecase of chlorination of fluorene to produce 9,9-dichlorofluorene it isvery important that chlorination of the aromatic rings be avoided.

Ida Smedley reported a preparation of 9,9-dichlorofluorene in 1905 fromheating fluorenone and a slight excess of phosphorus pentachloride (J.Chem. Soc. 87, 1249 (1905). Smedley did not report a yield, but didmention that the product contained fluorenone and requiredrecrystallization from benzene. Ray et al. repeated Smedley's method andattained a 66 weight percent yield. (J. Amer. Chem. Soc., 70, 1954(1948).) Ray et al report that the pure product is quite stable ifprotected from moisture, but that samples of impure material decomposedwithin a week to give a sticky green-yellow mass with the sharp odor ofhydrogen chloride.

Chlorinations of compounds having acidic protons and a molecularstructure which can delocalize the electron density of the conjugatebase such as fluorene using common chlorination agents such as chlorine,sulfuryl chloride, N-chlorosuccinimide and phosphorus pentachloride aregenerally disadvantageous because the products of such reactions exhibitsubstitution on the aromatic rings, instead of substitution of theacidic protons. Therefore, it is not feasible to prepare9,9-dichlorofiuorene from fluorene using conventional chlorinationtechnology.

A procedure for the preparation of 9,9-dichlorofluorene directly fromfluorene, without fluorenone as an intermediate, was reported by Reeveset al. in Israel J. Chem. 26, 225, (1985). Tetrabutylammonium bromidewas used as a phase transfer catalyst to chlorinate such compounds asfluorene, phenylpropanone, acetophenone, 1-chloroacetophenone,p-methoxyacetophenone, benzoin ethyl ether, p-nitroacetophenone,deoxybenzoin, and xanthene using carbon tetrachloride in an organicphase as chlorine source with an aqueous hydroxide phase. It wasreported that use of potassium carbonate in the aqueous phase in theattempted chlorination of p-nitroacetophenone resulted in no reaction.Using this reaction for the chlorination of fluorene, Reeves et al.reported a 51.9 percent yield of 9,9-dichlorofluorene. Other reactionconditions and time for the chlorination of fluorene are not given. A 57percent yield was reported by Reeves for production of xanthone fromxanthene using the procedure.

It would be desirable to have a selective process for chlorinatingcompounds which have acidic protons and a molecular structure which candelocalize the electron density of the conjugate base such thatreplacement of the acidic hydrogens is the predominant reaction but ingreater yields and/or shorter reaction times than those achieved whenfollowing the process reported by Reeves et al.

9,9-Bis(hydroxyphenyl)fluorene is typically prepared from fluorenonesuch as by reaction of fluorenone with phenol in the presence of suchcompounds as beta-mercaptopropionic acid and anhydrous hydrogen chloride(P. W. Morgan, Macromolecules, 3, 536 (1971); or in the presence of zincchloride and anhydrous hydrogen chloride (U.S. Pat. No. 4,467,122).Alternatively, fluorenone has been converted to 9,9-dichlorofluorene andsubsequently reacted with phenol to produce the9,9-bis(hydroxyphenyl)fluorene, such as by the reactions reported bySmedley in J. Chem. Soc. 87, 1249 (1905). All these reported methodsinvolve use of fluorenone to prepare 9,9-bis(hydroxyphenyl)fluorene.

It would be desirable to have a process for preparation of suchbisphenols as 9,9-bis(hydroxyphenyl)fluorene without using fluorenone asa reactant because preparation of fluorenone involves loss of startingmaterials, additional steps which may be time-consuming, and optionally,use of unpleasant starting materials. For instance, fluorene may beconverted to fluorenone by use of sodium dichromate to achieve about a60-70 percent yield. A higher yield is reported by Alneri, et al.Tetrahedron Letters, 24, 2117 (1977), but requires 24 hours. Amultiphase system involving an organic phase, an aqueous sodiumhydroxide phase and a catalyst of elemental carbon and phase transfercatalyst has also been reported in U.S. Pat. No. 4,297,514 (K. Ma) buthas the disadvantage of handling a solid and separating a product fromit. In each instance the fluorenone product must be isolated andpurified before subsequent reaction. It would be desirable to avoid suchextra steps.

SUMMARY OF THE INVENTION

The invention is a process for chlorinating at least one compound havingacidic protons and a molecular structure which can delocalize theelectron density of the conjugate base comprising contacting saidcompound with at least one perchloroalkane and aqueous base in thepresence of a phase transfer catalyst which is a tetraalkylammoniumhydroxide.

The process of the invention is particularly useful for chlorinatingcompounds having acidic protons and a molecular structure which candelocalize the electron density of the conjugate base compounds such asfluorene, which with conventional chlorination procedures will notreplace the acidic protons with chlorine.

When used to prepare such dichloro compounds as 9,9-dichlorofluorene,the process leads to an especially preferred process of alkylatingphenols, phenolics, aromatic amines, alkylaromatics and other sucharomatic compounds to give valuable polymers, oligomers, intermediatesand monomers, particularly, bis(hydroxyphenyl)fluorene.

DETAILED DESCRIPTION OF THE INVENTION

The process of the invention is useful for chlorinating compounds whichhave acidic protons and a molecular structure which can delocalize theelectron density of the conjugate base. It has been stated by Reutov et.al. (O. A. Reutov, I. P. Beletskaya and K. P. Butin, CH-ACIDS, PergamonPress. New York, N.Y., 1978.) that "almost any organic compound canionize in solution to give carbanions, that is, negatively chargedspecies whose charge is totally or more often partially localized on oneof the carbon atoms." When certain substituents are part of thehydrocarbon structure and are bonded to a saturated carbon atom whichalso bears hydrogen atoms, these hydrogen atoms are relatively acidic.Examples of such substituents are unsaturated functional groups such asvinyl, nitro, carbonyl, cyano, sulfone, or phenyl groups. The inductiveelectron withdrawing ability and the ability of these substituents todelocalize the negative charge remaining when a proton has been removedare responsible for the acidity of these carbon-hydrogen bonds. Thesecompounds are often referred to as active methylene (--CH₂ --) or activemethine (--CH--) compounds. Active methylene compounds are preferred foruse in the practice of the invention; more preferred are compoundshaving an active methylene group adjacent to at least one vinyl, nitro,carbonyl, cyano, sulfone, cyclopentadiene, or phenyl group, mostpreferably adjacent to at least two such groups which may be the same ora combination thereof. Exemplary of such compounds are fluorene,ring-substituted fluorenes, indene, xanthene, anthrone, phenalene,chromene, acetone, acetophenone, deoxybenzoin, phenylacetonitrile,cyclopentadiene, dihydroanthracene, 1-phenyl-2-propanone,alkylpyridines, alkylpyrazines, alkylquinolines, alkylisoquinolines,alkylquinoxalines, alkylquinazolines, alkylcinnolines and the like. Theprocess of the invention is particularly useful for compounds for whichthe replacement of the acidic protons with chlorine is not easy underconventional chlorination conditions including fluorene, indene,xanthene, anthrone and the like, preferably fluorene and its derivativeswhich are ring-substituted, most preferably fluorene. Such targetcompounds are unsubstituted or inertly substituted, that is havingsubstituents which do not undesirably interfere with the chlorination orsubsequent reactions. Such substituents include alkyl, halo, nitro,cyano, carboxyl, thio, sulfoxide, sulfone, carbonyl, ether, and arylgroups, as well as other substituents not having a hydroxyl, primary orsecondary amino, or mercapto group. Preferably the compounds have fromabout 5 to about 30 carbon atoms and more preferably at least one arylgroup which is preferably carbocyclic, preferably of from about 6 toabout 20 carbon atoms or heterocyclic of from about 5 to about 20 carbonatoms and at least one oxygen, sulfur, nitrogen, selenium, silicon, orother heteroatom.

The target compound is chlorinated by contacting it with aperchloroalkane such as carbon tetrachloride, hexachloroethane, orbenzotrichloride and the like as the chlorine source. Carbontetrachloride is the preferred chlorine source and is used herein toexemplify perchloroalkanes, but not to limit the process thereto. Theperchloroalkane is suitably used in any amount which provides sufficientchlorine for the reaction, and may also be present in an amountsufficient to dissolve the compound being chlorinated (target compound).It is, however, unnecessary that there be sufficient perchloroalkane todissolve the target compound. When the compound to be chlorinated has alow solubility in the perchloroalkane, it is preferable to use a solventmiscible in the perchloroalkane which dissolves significant amounts ofthe target compound. Preferably the perchloroalkane is used in an amountfrom about 1:1 to about 100:1 based on the molar concentration ofreactant (target compound), more preferably from about 2:1 to about50:1, most preferably from about 2:1 to about 10:1 based on the molarconcentration of the target compound.

When an additional solvent is used, it is preferably one which ismiscible with the perchloroalkane and which dissolves the targetcompound and, conveniently, is not undesirably affected by the reactionconditions. Such solvents include methylene chloride, ethylbenzene,cumene, chlorobenzene, tetrahydrofuran and the like. Such a solvent isconveniently used in an amount sufficient to obtain the maximumconcentration of the target compound but not so little that the productwould precipitate from the reaction mixture.

The target compound is contacted with the perchloroalkane in thepresence of a base strong enough to deprotonate the target compound,that is, capable of forming the conjugate base of the target compound.Such bases include inorganic and organic hydroxides and any other strongbases compatible with water, preferably alkali metal hydroxides ortetraalkylammonium hydroxides more preferably alkali metal hydroxides,most preferably sodium hydroxide. Alkali metal hydroxides are preferredbecause they have good solubility in water and relatively low equivalentweight. Sodium hydroxide is more preferred because of commercialavailability. The base is advantageously in aqueous solution because ofease of removal from product. The solution is suitably of aconcentration sufficient to promote the reaction at a desirable rate,preferably from about 10 percent to about 80 percent, more preferablyfrom about 20 percent to about 50 percent, most preferably from about 30percent to about 40 weight percent base in water. Sodium hydroxidesolutions of 40 percent and above often result in emulsions which aredifficult to handle. The aqueous solution of base and perchloroalkaneare suitably present in any ratio sufficient to promote the reaction ata desirable rate. A desirable rate is generally one sufficient tocomplete the reaction in the desired time, but insufficient to causeexcessive or uncontrollable exothermic heating of the reaction mixture.

Contrary to the teachings of Reeves et Israel J. Chem. 26, 225, (1985)wherein a large excess of base was used with a tetrabutylammoniumbromide phase transfer catalyst, in the process of the invention it issurprisingly observed that much less than an equivalent of base isneeded. The preferable amount of base as a function of the concentrationof the target compound is 0.001 to 1000, more preferably from about 0.01to about 100, most preferably from about 0.1 to about 10 molar ratio.Less than a stoichiometric amount of base is preferred because it leavesmore room in the reactor to make product and there is less base todispose of after the reaction.

Because the target compound is not sufficiently soluble in the aqueousbase, a phase transfer catalyst is used. Surprisingly good yields andlow reaction times are noted when the phase transfer catalyst is atetraalkylammonium hydroxide such as tetrabutylammonium hydroxide,tetramethylammonium hydroxide, tetraethylammonium hydroxide,tetrapropylammonium hydroxide, benzyltrimethylammonium hydroxide,tributylmethylammonium hydroxide and the like, or atetraalkylphosphonium hydroxide such as tetrabutylphosphonium hydroxide,tetrapropylphosphonium hydroxide, (together tetraalkylonium hydroxide),preferably the phase transfer catalyst is a tetraalkylammonium hydroxidewherein all alkyl groups have from about 1 to about 20 carbon atoms andare nonaromatic, more preferably the tetraalkylammonium hydroxide istetrabutylammonium hydroxide or tributylmethylammonium hydroxide, mostpreferably tetra-n-butylammonium hydroxide because this catalyst bringsthe reaction to completion in the shortest time with the least amount ofcatalyst relative to the target compound.

The phase transfer catalyst is suitably present in any amount sufficientto give a desired rate of reaction, advantageously at least about 0.000mole ratio, preferably from about 0.0001 to about 1, more preferablyfrom about 0.001 to about 0.1, most preferably from about 0.001 to about0.05 molar ratio based on the number of moles of the target compoundbecause this amount gives an acceptable rate of reaction and using moregenerally costs more and makes purification of the product moredifficult. While the hydroxide phase transfer catalyst is optionallyadmixed with other phase transfer catalysts, e.g. the halide salts, thephase transfer catalyst is preferably present in the hydroxide salt formin at least the concentrations noted.

The concentrations indicated are preferably that of the phase transfercatalyst in the form of the hydroxide salt. Although theoretically phasetransfer catalysts having other anions could convert into the hydroxidewhen hydroxide ions are present, such a conversion is not generallyobserved. Quaternary ammonium salts are true ionic species in aqueousmedia and behave as salts much like the alkali halides. Thus, in anaqueous solution, the quaternary ammonium salts are present as ion pairsand freely undergo ion exchange with other ions in solution. When aquaternary ammonium salt is employed as a catalyst in a two phasereaction system, the concentration of that salt in the separate phasesis dependent on the relative solubility of the salt in each phase. Whenphase transfer catalysts having two or more types of anion are present,the relative concentrations of quaternary ammonium salts may becalculated from the extraction constants for the salts and solvents ofinterest. Extraction constants (E_(QX)) for systems Q⁺ _(aq) ^(+X-)_(aq=QX) _(org) (concentrations of quaternary ions in aqueousphase+anion in aqueous phase is in equilibrium with quaternary salt inorganic phase) are defined by

    E.sub.QX =(QX).sub.org /(Q.sup.+).sub.aq (X.sup.-).sub.aq

where Q⁺ is the quaternary ammonium cation, X⁻ is the anion, and QX isthe quaternary ammonium salt of interest. When two ions are present, theextraction equilibrium K defined as

    K=E.sub.QY /E.sub.QX =(QY).sub.org (X.sup.-).sub.aq /(QX).sub.org (Y.sup.-).sub.aq

(where X⁻ and Y⁻ are different anions) defines the relative amounts ofthe quaternary ammonium salts that will be present in the organic phase.DehmLow (E. V. DehmLow, M. Slopianka, and J. Heider, Tetrahedron Lett.,1977, 2361.) has measured this value by equilibrating tetran-butylammonium chloride with 50 percent NaOH solution and found that ofthe tetra n-butylammonium ion present in the organic phase only 4.2percent was present as the hydroxide form, the remainder being presentas the chloride. The extraction constants for tetra n-butylammoniumchloride (E_(QX) =1.00), tetra n-butylammonium bromide (E_(QX) =48.5)and tetra n-butylammonium hydroxide (E_(QX) =0.01) are reported byGustavi (K. Gustavi and G. Schill, Acta Pharm. Suec., 3 259, (1966) inA. Brandstrom, Principles of phase transfer catalysis by quaternaryammonium salts, in "Advances in Physical Organic Chemistry," Vol 15, V.Gold, Ed., Academic Prss, London and New York, 10977, page 281). Usingthese values we may calculate that when tetra n-butylammonium bromide isequilibrated with 50 percent NaOH only 0.086 mole percent of the tetran-butylammonium ion present in the organic phase is present as thehydroxide form, the remainder being present as the bromide.

Thus, since the hydroxide form of the phase transfer catalyst isobserved to be, very surprisingly, more effective than the bromide form,it is evident that the hydroxide form is preferably present in aconcentration greater than about 0.09 mole percent, more preferablygreater than about 0.1 mole percent, most preferably greater than about1 mole percent of the total phase transfer catalyst. Even morepreferably at least about 10 percent of the phase transfer catalystpresent is in the hydroxide salt form. Also, the chlorination process ofthe invention preferably takes place in the presence of insufficientbromide or other ion that would extract the tetraalkylammonium ion intothe organic phase to reduce the concentration thereof in the aqueousphase below that concentration achieved by the hydroxide salt at thepreferred concentrations. Most preferably, the reaction takes place inthe substantial absence of bromide ion--that is in the absence of addedbromide anion.

Conveniently, the compound to be chlorinated is dissolved in theperchloroalkane, to which are added the aqueous base and phase transfercatalyst either sequentially in either order, simultaneously butseparately or in admixture to form a reaction mixture. This order isconvenient because it is observed that the solution of the compound inperchloroalkane is conveniently purged, e.g. with an inert gas such asnitrogen, helium, argon, neon, or hydrogen to remove oxygen to avoidproduction of an oxidized target compound as a by-product.Alternatively, the reagents are suitably mixed in any order such thatall reactants are present at one time. The reaction mixture ispreferably agitated by any means effective to maximize the surface areaof the immiscible phases so that the reactants in each phase arerepeatedly brought together.

When ketone products are not desired it is often preferable to excludeoxygen from the reaction. Oxygen is suitably excluded by any meanswithin the skill in the art such as by maintaining a nitrogen blanketover the reaction mixture, such as by nitrogen sparging. Other inertgasses or the vapors of highly volatile organic compounds may beemployed.

Any reaction conditions under which the chlorination takes place aresuitable, but preferred temperatures are from about 0° C. to about 100°C., more preferably from about 15° C. to about 80° C., most preferablyfrom about 25° C. to about 40° C. because at these temperatures thereaction proceeds rapidly and there is little degradation of thecatalyst. Any effective pressure is suitable, at or near atmosphericpressure is generally convenient. High pressure is not harmful. Lowerpressures are limited by the vapor pressures (boiling points) of thesolvents employed.

Good mixing is important for rapid reaction. For instance at a moleratio of sodium hydroxide to fluorene of 10:1; mole ratio oftetrabutylammonium hydroxide to fluorene of 0.02:1.0; mole ratio ofcarbon tetrachloride to fluorene of 2:1 and 25 weight percent fluorenein methylene chloride at 30° C. for the indicated times, the followingtable indicates the importance of stirring on yield of9,9-dichlorofluorene (9,9-DCF).

    ______________________________________                                               at           at          at                                                   500 RPM      1500 RPM    3000 RPM                                             percent      percent     percent                                              9,9-DCF      9,9-DCF     9,9-DCF                                       TIME   corresponding                                                                              corresponding                                                                             corresponding                                 (minutes)                                                                            to 0.8 W/L   to 19.7 W/L to 106 W/L                                    ______________________________________                                        0      0            0           0                                             1      73.1093      84.8193     95.7622                                       2      80.2118      89.1515     96.7862                                       3      84.6704      91.7289     97.1994                                       4      89.3134      93.3434     98.1167                                       5      91.7465      93.5317     98.1575                                       10     94.8384      95.7186     98.9512                                       15     96.2824      97.4078     99.053                                        20     96.9075      97.4977     99.0207                                       30     97.177       97.4588     99.086                                        60     98.1961      98.47       99.3304                                       120    96.3133      97.3576     99.0197                                       ______________________________________                                    

Thus, for relatively shorter reaction times, relatively faster mixing ispreferred. While mixing is difficult to quantify, in a situation withrelatively constant viscosities, power per unit volume (watts per liter)is indicative of the amount of mixing. These values were obtained usinga Lightnin™ LabMaster II™ Model TSM2010 Mixer commercially availablefrom Mixing Equipment Company, Avon Division, a unit of General Signalwhich directly measures the watts input into the mixer. Thus, in thepractice of the invention, mixing preferably involves use of at leastabout 0.8 W/L, more preferably at least about 15.0 W/L, most preferablyat least about 100 W/L. Such mixing is suitably accomplished by anymeans within the skill in the art such as by rotary, static (e.g.recirculating, e.g. by pump) or other mixing.

The reaction is preferably carried out using non-metallic vessels andequipment, that is not having exposed metals, because metals such asiron (including steel, even stainless steels such as those designated as304 or 316 stainless steel), nickel and titanium are observed to inhibitthe reaction. The term non-metallic vessels and equipment is used toinclude vessels and equipment lined with non-metallic materials such aspolymers (including plastics, resins and glass). Thus the reactionpreferably occurs in the substantial absence of such metals, that is inthe absence of sufficient metal to undesirably inhibit the reaction,more preferably in the absence of other than incidentally present (notdeliberately added) metals particularly iron, including 304 stainlesssteel and 316 stainless steel. These metals are believed to inhibit thetetraalkylammonium hydroxides; thus use of additional tetraalkylammoniumhydroxide to replace that which is inhibited permits reaction in thepresence of metals.

The product can be isolated by means within the skill in the art,preferably by washing the solution with water to remove catalyst, thenevaporating the solvent. Products are usually solids and are optionallypurified by crystallization.

The reaction is allowed to go to a predetermined degree of completeness,advantageously to completion as determined by cessation of an increasein concentration of product. At temperatures such as about 30° C.,completion is observed after about 1 minute to 3 hours depending oncatalyst concentration, caustic concentration, and degree of agitationor mixing.

The catalyst (tetraalkylonium hydroxide) and/or the base (inorganic ororganic hydroxides) are, optionally, conveniently recycled to preparegem dichloro compounds through many reaction cycles with no loss inefficacy. The catalyst is easily recovered from the reaction mixtureafter completion of the reaction by means known to those skilled in theart, such as extraction with water or other immiscible solvent havinggood solubility for the tetraalkylonium hydroxide, or alternatively bycontacting the reaction solution with an acidic ion exchange resin toretain the catalyst as a salt followed by regeneration of thetetraalkylonium hydroxide by contacting the ion exchange resin with anaqueous hydroxide solution. In either case, the catalyst is convenientlyisolated by evaporative removal of the solvent or is simply used withoutisolation if the concentration and the solvent are appropriate for thedesired reaction. Reuse of the base is, for instance, accomplished byphase separation of the organic and aqueous phases after completion ofthe reaction and admixing or contacting fresh organic reaction mixturewith the separated aqueous phase. Catalyst, either fresh or recovered,is then supplied and the reaction repeated. Recycle of catalyst and/orbase is a major advantage since it reduces the amount of raw materialsneeded with corresponding reduction of waste to dispose.

When the chlorination process is used to prepare a dichloro compound,preferably 9,9-dichloro-fluorene, dichlorocyclopentadiene,1,1-dichloroindene, 9,9-dichloroxanthene, 9,9-dichlorothioxanthene,1,1-dichlorophenalene, 11,11-dichloro-4,5-methylenephenanthrene,p-biphenylyldiphenyldichloromethane, dichlorophenylpropanone,4,4-dichloro-4,H-chromene, dichlorodeoxybenzoin, dichloroacetophenone,1,1-dichloroacetone, more preferably 9,9-dichlorofluorene, it isparticularly beneficial to react the dichloro compound with a compoundhaving an activated (electron rich) aromatic structure such as a phenol,an aniline, a phenolic, a polyphenolic, an aromatic hydrocarbon such astoluene, anisole, indene, xylene, ethylbenzene, dimethoxybenzene,thiophene, furan, pyrole and the like. The term "dichloro compound"includes compounds having at least one gem-dichloro group (two chlorineatoms on the same carbon) including such compounds astetrachloroanthracene, as produced by chlorination of dihydroanthraceneby practice of the invention.

Dichloro compounds such as 9,9-dichlorofluorene, are reactive inalkylation and can be reacted with aromatic compounds to form e.g.9,9-diarylfluorenes where aryl substituents replace the chlorine atomsof the dichloro group(s). For simplicity, this aspect of the inventionis explained in terms of aromatic derivatives of 9,9-dichlorofluorene,but the invention is not limited thereto and is applicable to alldichloro compounds such as are prepared by the process of the invention.Such compounds can be reacted with any aromatic compound which isreactive toward electrophilic aromatic substitution. These includearomatic compounds substituted with activating groups such as alkoxy,alkyl, hydroxy, or amino groups, as well as aromatic compoundssubstituted with weakly deactivating groups such as halo, ester, ketone,anhydride, or haloalkoxy groups. Reaction of e.g. 9,9-dichlorofluorenewith two equivalents of an activated aromatic substrate can form e.g. a9,9-diarylfluorene compound. For less activated aromatic substrates itis advantageous to use an excess of the aromatic substrate to producee.g. a 9,9-diarylfluorene compound. Reaction of dichloro compounds suchas 9,9-dichlorofluorene with an approximately equimolar amount of asuitably reactive aromatic substrate produces a polymer. To avoidcrosslinking through the aromatic portion of a dichloro compound duringthe alkylation reaction with a dichloro compound to form monomers,oligomers, and polymers, the aromatic substrate should be more activatedto alkylation than the dichloro compound itself. Activated aromaticcompounds such as those having ether, hydroxyl or amine substituents canreact with such compounds as 9,9-dichlorofluorene without the additionof a Lewis acid catalyst. Although the reaction proceeds without addedcatalyst, less activated aromatic compounds react more efficiently withthe addition of an acid catalyst. Suitable protic and Lewis acidcatalysts include, but are not limited to, HCl, AlCl₃, FeCl₃, SbCl₅, H₂SO₄, CH₃ SO₃ H, EtAlCl₂ (ethyl aluminum chloride), BF₃, ZnCl₂, GaCl₃ ;calcined sulfate salts of Fe, Zn, Co, Mn, and Cu; AlCl₃ --CH₃ NO₂,SnCl₄, TiCl₄, the metal alkanoates commonly known as paint driers suchas iron naphthenate, zinc octoate, cobalt naphthenate, tin octoate, andsimilar such compounds, and polymeric acid catalysts including ionexchange resins, fluorine-containing sulfonic acid catalysts, acidicclays, zeolites, oxides of aluminum and silica. Lewis acid catalysts areoptionally generated in-situ by reaction of active metals such as Al,Zn, Fe with HCl either added or formed as a byproduct of the reaction.Examples of aromatic compounds which can be alkylated with suchcompounds as 9,9-dichlorofluorene include toluene, xylene,2-aminophenol, ethylbenzene, indene, benzocyclobutane, anisole, phenol,aniline, 2-bromotetrafluoroethoxybenzene, bromobenzene, chlorobenzene,fluorobenzene, phenyl acetate, acetophenone and the like. Examples ofaromatic compounds which can be alkylated with such compounds as9,9-dichlorofluorene to form polymers include phenyl ether, phenylcarbonate, dimethoxybenzene, diphenyl amine, benzene, xylene, durene,poly(phenylene ethers) and substituted derivatives thereof where thesubstituents do not deactivate the aromatic compounds such that nopolymer is formed. The dichloro and aromatic compounds are suitablyunsubstituted or inertly substituted, that is having substituents whichdo not undesirably interfere with the alkylation. Such substituentsinclude alkyl, alkoxy, halo, nitro, cyano, carboxyl, thio, sulfoxide,sulfone, carbonyl, ether, aryl, ester, anhydride, and ketone groups.

Any compound reactive with the dichloro compound is suitably reactedtherewith. Exemplary phenolic compounds include any phenolic orthiophenolic compound which reacts with the dichloro compound, includingalkylphenols, cresol, chlorophenol, isopropylphenol, propylphenol,2,6-dimethylphenol, naphthol, xylenol, dichlorophenol, phenylphenol,resorcinol, catechol, hydroquinone, aminophenols, hydroxybiphenyl,hydroxyacetophenone, allylphenols, dialkylphenols, thiophenols,nitrophenols, halophenols, naphthols, hydroxybiphenyls, nonylphenol andethylphenol, preferably o-, m- and p-cresols, 2,6-dimethylphenol, o- andm-chlorophenols, 2-naphthol, 1-naphthol, 3,4-xylenol or3,4-dimethylphenol, 2-methylthiophenol, 2-nitrophenol, 3-nitrophenol,4-nitrophenol, 2-aminophenol, 3-aminophenol, 4-aminophenol,2,6-dimethylphenol, 2,6-dichlorophenol, 3,5-dichlorophenol,3,4-dimethylphenol, o-, m- and p-cresols and pyrogallol, more preferablyphenol, aminophenol, methoxyphenol, o-hydroxyacetophenone,2,6-dimethylphenol, 2,6-dichlorophenol, 3,5-dichlorophenol, andpyrogallol, most preferably (unsubstituted) phenol, 2,6-dimethylphenol,2,6-dichlorophenol, 3,5-dichlorophenol, 3,4-dimethylphenol, o-, m- andp-cresols and pyrogallol. Alkyl and dialkyl phenols preferably havealkyl groups of from about 1 to about 50 carbon atoms, more preferablyfrom 1 to about 10 carbon atoms, and are suitably cyclic, straight chainor branched.

Exemplary aniline compounds include unsubstituted aniline,N-alkylanilines, alkylanilines, dialkylanilines, o-, m-,p-phenylenediamine, chloroanilines, phenylanilines, N-methylaniline,methylaniline, 2,6-dimethylaniline, 2-chloroaniline, toluenediamine,methylenedianiline, polymeric methylenedianiline, 2,6-dichloroaniline,and ethylaniline.

Exemplary aromatic hydrocarbon compounds include toluene, benzene,ethylbenzene, biphenyl, xylene, trimethylbenzene, durene, napthalene,indene, benzocyclobutane, diethylbenzene, dialkylbenzenes, furans(particularly methyl and chloro substituted) and thiophenes(particularly methyl and chloro substituted).

Exemplary aromatic ether compounds include anisole, methylanisole,phenyl ether, dimethoxybenzene, biphenyl ether, diphenoxybenzene,4,4'-diphenoxy phenylether and naphthyl ether.

Exemplary halogenated aromatic compounds include chlorobenzene,fluorobenzene, and bromobenzene.

Exemplary aromatic ester compounds include phenyl acetate, phenylcarbonate, methyl benzoate, methylsalicylate, and phenyl benzoate.

Other exemplary aromatic compounds include acetophenone, and phthalicanhydride, as well as heterocyclic compounds including furan, methylfuran, chlorofuran, benzofuran, thiophene, methylthiophene,chlorothiophene, pyrrole, methyl pyrrole, and chloropyrrole.

Derivatives of the listed compounds such as the acetamide or maleimidederivative of aniline or the listed anilines are similarly useful. Forinstance, the N-phenylmaleimide is useful to prepare bismaleimides whichare useful as monomers for certain addition polymers. Similarly, theacetamide derivative of aniline may be used in place of aniline.

Alternatively, the dichloro compounds may be reacted with compoundswhich have at least two aromatic rings connected by a bond or a bridgeof one atom which is optionally substituted, as illustrated by:

aromatic-X-aromatic

wherein "aromatic" stands for any aromatic group, including any suitablefor use in the aromatic compounds not having a bridge, and X stands fora bond or any bridging group such as --O--, --S--, --CO--, --CH₂ --,--NH--, --PR--, --SO₂ --, --SO--, --Se--, --SiR₂ --, and the like, whichare also optionally substituted, e.g. --NR--, --CR₂ --, --CHR--, where Ris any group, preferably an optionally inertly substituted hydrocarbylgroup, more preferably a hydrocarbyl or fluorocarbyl group of from about1 to about 6 carbon atoms. Such compounds are advantageously substitutedsuch that dialkylation of the dichloro compounds onto these compoundsoccurs with the formation of a 5- or 6-membered ring, preferably betweenaromatic rings, more preferably including the bridging group X and thecarbon of a gem-dichloro group in the dichloro compound. For this typeof cyclization, it is preferred that substitution on the aromaticcompound be such that alkylation ortho to the --X-- group is favored.For example, where the presence of --X-- would favor alkylation ortho orpara to --X--, such as wherein --X-- is --O--, --S--, or a bond, it isadvantageous for the compound to be substituted in the para positionwith an activating or deactivating group such that alkylation ortho to--X-- becomes the favored reaction. Compounds of this type include4,4'-thiodiphenol, 4,4'-oxydianiline, 4,4'-thiodianiline, and4,4'-diphenic acid. It is also advantageous to not only be substitutedin the para position, but also to have additional substitutents whichfurther activate the position ortho to --X-- to alkylation. Compounds ofthis type include 3,3',4,4'-tetraaminobiphenyl, 3,3'-dimethoxybenzidine,3,3'-dihydroxy-4,4'-diaminobiphenyl, and 3,3'-dimethylbenzidine. Wheresuch additional substituents do not activate the position ortho to --X--to alkylation, it can be advantageous to have additional substituentssuch that alternate positions which would have been active towardalkylation are already substituted and therefore, blocked. Compounds ofthis type include tetrabromobisphenol A. When the nature of the --X--group is such that alkylation ortho to this group is not favored, suchas wherein --X-- is --CO--, --SO₂ --, or --SO--, it is advantageous thatthe compound be substituted meta to --X-- with groups which willactivate the position ortho to --X-- to alkylation. Compounds of thistype include 3,3'-diamino-4,4'-diphenylsulfone,3,3'-dimaleimido-4,4'-diphenylsulfone, and 3,3'-diaminobenzophenone.Exemplary compounds for the formation of such cyclized products includebismaleimide (1,1'(methylenedi-4,1-phenylene)bismaleimide),4,4'-diphenic acid, biphenyl tetracarboxylic dianhydride,4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-diphenylsulfone,3,3'-dimaleimidodiphenylsulfone, 3,3'-4,4'-tetraaminobiphenyl,3,3'-diaminobenzophenone, bis(4-fluorophenyl)methane, o-tolidine(3,3'-dimethylbenzidine), hisphenol F, tetramethylbisphenol F,4,4'-thiodiphenol, 4,4'-oxydiphenol, 4,4'-oxydianiline,4,4'-oxydiacetanilide (e.g. made by reaction of 4,4'-oxydianiline withacetyl chloride), 4,4'-thiodianiline, 4,4'-thiodiacetanilide (e.g. madeby reaction of 4,4'-thiodianiline with acetyl chloride),3,3'-dimethoxybenzidine, 3,3'-dimethylbiphenyl, and1,1-bis(3,4-dimethylphenyl)ethane. While cyclization advantageouslytakes place under the reaction conditions useful for alkylation(reaction of dichloro and aromatic compounds), especially when thoseconditions are acidic; additional acid is useful when the conditions areless acidic, particularly when the aromatic compound isamine-substituted, e.g. an aniline, and when little or no acid catalystis used.

The dichloro compounds are also reactive with aromatic compoundssubstituted such that cyclization to form 5- or 6-membered rings occursduring or subsequent to the alkylation reaction. Exemplary compounds forthe formation of such cyclized products include resorcinol,hydroquinone, hisphenol A, biphenol, m- and p-phenylenediamine,p-aminophenol, m-aminophenol and mixtures thereof.

In the discussions of aromatic compounds, most illustrations of aromaticrings have been phenyl groups, however, while phenyl rings are preferredfor their wide availability, the rings are suitably fused and/orheterocyclic rings such as furans, thiophenes and pyrrole. The aromaticcompound preferably has from 5 to about 20 ring atoms, at least 4 ofwhich are preferably carbon atoms, with heteroatoms in the ring(s)suitably any atom which forms a ring compound with carbon, butpreferably selected from O, S, N, and phosphorus, all optionallysubstituted such as SO₂, NH, --PR₂ or --P(═O)R₂, where R is alkyl oralkoxy preferably of from about 1 to 10 carbons. More preferably thering has from about 6 to about 13 ring atoms, all most preferablycarbon.

As one example of the use of multicyclic aromatic compounds, thedichloro compounds are optionally reacted with polyphenolic materialsuch as novolac resins produced as reaction products of such aromatichydroxyl compounds as phenol, cresol or xylenol with an aldehyde,preferably formaldehyde, to produce resinous products. The novolacs areadvantageously kept at stoichiometric equivalent or excess to thedichloro compounds. These modified polyphenolics are useful as curingagents for polyepoxy compounds, and as starting materials for producingpolyepoxies and polycyanates.

To modify the reactivity, processability, or thermal and mechanicalproperties of the resultant products, dichloro-compounds and aromaticcompounds are optionally reacted in suitable ratios to form oligomericproducts which are useful for further reaction to form polymericmaterials or which are optionally terminated with the same or differentaromatic compounds. By increasing the ratio of the dichloro compound toaromatic compound greater than that ratio sufficient to replace bothchlorine atoms by aromatic compound, oligomers terminated with endgroups containing a resulting mono-chloro compound are produced. Forexample, reaction of 9,9-dichlorofluorene with phenyl ether in a molarratio of about 3:2 will produce a mixture of oligomers wherein theterminal fluorene groups retain a 9-chloro functionality. Reacting thisoligomeric mixture with an excess of phenol will produce a phenolicoligomer suitable for conversion into a polymer. Reacting the 9-chloroterminated oligomeric mixture with, for instance, a mixture of9,9-dichlorofluorene and phenyl carbonate in about 1:1:1 molar ratiowill produce a block copolymer. Reacting the 9-chloro terminatedoligomeric mixture with, for instance, benzocyclobutane, will produce abenzocyclobutanyl-capped oligomer suitable for use in formingbenzocyclobutanyl polymers. Similarly, these oligomeric compounds can befurther reacted by processes taught herein or within the skill in theart. Exemplary of aromatic compounds that can be used to form oligomerswhen reacted with dichloro compounds are phenyl ether, anisole,dimethoxybenzene, xylene, mesitylene, methylanisole, phenol, cresol,bisphenol A, bisphenol F, biphenol, phenol-aldehyde novolac resins,bisphenol S, biphenyl, phenylphenol, phenylthioether, and the like, andmixtures thereof.

Combinations of aromatic compounds are useful to react with the dichlorocompounds. Advantageously, when combinations of aromatic compounds arereacted with the dichloro compounds, they have similar reactivity withthe dichloro compounds such that the products of such reactions haveapproximately equal amounts of each aromatic compound distributedtherein. For instance, benzocyclobutane and N-phenylmaleimide arereacted with 9,9-dichlorofluorene to produce mixtures of9-(benzocyclobutanyl)-9-(maleimidophenyl)fluorene,9,9-bis(benzocyclobutanyl)fluorene, and9,9-bis(4-maleimidophenyl)fluorene. Similarly, o-allylphenol andN-phenylmaleimide are reactive with 9,9-dichlorofluorene to produce ananalogous mixture of compounds. Advantageously, when the aromaticcompounds have dissimilar reactivities or when certain predeterminedproducts or mixtures are desired, product mixture is controlled bystoichiometry of the mixture of aromatic compounds reacted or by use ofsequential reactions. Sequential reactions are particularly exemplifiedby the reaction of one mole of an aniline with a dichloro compoundaccording to the practice of the invention, which reaction produces amonoalkylation product; the monoalkylation product is then reacted withanother mole of aromatic compound, e.g. a phenol. Alternatively, themonochloro compound may be isolated and used in a separate application.For example, reaction of 9,9-dichloroxanthene with one equivalent ofbenzene produces 9-chloro-9-phenylxanthene, a deoxynucleoside5'-0-protecting reagent. Control by stoichiometry of reactants isexemplified by reaction of a dichloro compound with a mixture of onemole each of two aromatic compounds (illustratively referred to as A andB) to produce a product mixture of alkylation products with two moles ofB (BB), with two moles of A (AA), and with a mole of each (AB). Wheneven distribution of products is desired and the reactivities aredissimilar, those skilled in the art realize that use of an excess ofthe less reactive aromatic compound (the amount of excess determined bythe difference in reactivities) will result in a more evenly distributedproduct mixture than will use of equimolar quantities of the aromaticcompounds. Other predetermined proportions of products are obtained byuse of proportions of the aromatic compounds determined by theirrelative reactivities and the predetermined desired proportions.

The reaction between the dichloro compound and the aromatic compound(together, reactants) is suitably conducted with any reactant ratios andunder any conditions in which the compounds react, but, when monomericproducts are desired, preferably the aromatic is present in an amountsufficient to consume the chloro compound but insufficient to makeisolation of the product difficult, preferably from about 100:1 to about1:100, more preferably from about 50:1 to about most preferably fromabout 4:, to about 1:1 based on equivalents of chlorine to be replaced(aromatic compound equivalents to chlorine equivalents). When thearomatic compound is an aniline, the most preferred ratio is from about4:1 to about 2:1 moles of the aniline to moles of dichloro compound.When preparation of a polymer or oligomer is desired, reactant ratiosare suitably any sufficient to produce polymer or oligomer butinsufficient to produce mostly monomeric compound, preferably from about0.5:1 to about 1:0.5 more preferably from about 0.9:1 to about 1:0.9based on equivalents of chlorine to be replaced.

Reaction of dichlorofluorene with benzocyclobutane illustrates theutility of the oligomer forming reaction.9,9-bis(benzocyclobutanyl)fluorene is formed when a mole ofdichlorofluorene is reacted with a large excess (ten to thirty moles) ofbenzocyclobutane under conditions of mild temperature, e.g. roomtemperature to about 50°, and addition of the dichlorofluorene to anexcess of benzocyclobutane. However, when a mole of dichlorofluorene isreacted with less than ten moles of benzocyclobutane, oligomers areformed which generally have n benzocyclobutane groups and (n-1) fluorenegroups, resulting from disubstitution of some of the benzocyclobutanegroups with dichlorofluorene, where n is at least 2. The oligomers areuseful because they form low melting thermosettable compositions whichcan be cured thermally with no added catalyst and without the evolutionof volatiles. A useful variation of this chemistry is the use of anaromatic compound more reactive than benzocyclobutane, preferably anaryl ether such as anisole, diphenoxy phenyl ether, diphenoxy benzene ordiphenyl ether along with the benzocyclobutane to alkylate thedichtorofluorene. Thermosetting resins are formed having internaloligomeric sections which are made up of alternating fluorene and arylether moieties and are terminated with benzocyclobutane groups orfluorene-benzocyclobutane oligomeric sections. Oligomers havingbenzocyclobutane, more reactive aromatic compounds, especiallypolyphenylene ethers, and dichlorofluorene are useful to crosslink epoxyresins. Although the reactive oligomers containing benzocyclobutanerings are described in terms of fluorene derivatives, which areparticularly useful for this purpose, the fluorene is merelyillustrative of the gem-dichloro compounds previously described, all ofwhich, particularly the polycyclic dicloro compounds, are useful in theprocess.

This invention differs from current benzocyclobutane polymer (BCB)chemistry as illustrated by U.S. Pat. No. 4,540,763 (Kirchoff et al.).BCB chemistry typically requires the use of bromo-benzocyclobutane as astarting material. Bromination of benzocyclobutane hydrocarbon adds anadditional step and produces waste products, thus adding a significantcost to the final resin products. Alternatively, the benzocyclobutanehydrocarbon is used in the acylation of the hydrocarbon with a diacidchloride and an equivalent amount of Lewis acid (to the carbonyls, i.e.to acylate a diacid chloride onto benzocyclobutane requires two moles ofLewis acid for every mole of diacid chloride). The present inventiondiffers from that technology in that only catalytic amounts of Lewisacid are used. Use of little Lewis acid simplifies a synthesis process,not only in the amount of waste generated, but also in the ease ofseparating the catalyst from the desired product.

When analogous oligomeric mixtures are made from the reaction of adichloro compound, e.g. dichlorofluorene, with alkylaromatics such astoluene, cumen, xylenes, trimethylbenzene, and the like, the oligomericmixtures are advantageously oxidized by means within the skill in theart to form polyacids and/or polyanhydrides, useful as monomers forinstance to make polyglycol esters useful in polyurethanes.

The reactants are suitably used neat or in solution. When used neat,they are preferably liquids, but may alternatively be used in the solidstate by means within the skill in the art such as by mixing or grindingthe finely divided solids together in a mill or blender under conditionsof high shear. Especially when at least one reactant is solid, a solventis used, suitable solvents include any solvent for at least one of thereactants, preferably for both, and preferably which does not interferewith the reaction or react with either reactant. Preferred solventsinclude carbon tetrachloride, chloroform, methylene chloride, ethylenedichloride, trichloroethane, tetrachloroethane (any common chlorinatedsolvents); aromatic hydrocarbons such as benzene, toluene, ethylbenzene;chlorinated aliphatic compounds; aromatic ethers such as phenyl ether;ethers, ketones, esters, amides, sulfoxides, alcohols, alkanoic acids,halogenated aromatics such as chlorobenzene; tetrahydrofuran; aceticacid and nitriles such as acetonitrile, more preferably dichloromethane,carbon tetrachloride, ethylbenzene, toluene or chlorobenzene.

While suitable reaction conditions include any effective conditions,including temperatures of from subambient to several hundreds of degreescentigrade; preferably temperatures used are less than the boilingpoints of any reactants under the pressure used. Conveniently, when asolvent is not used, the temperature is sufficient to allow at least onereactant to be liquid. Preferred temperatures range from about -30° C.to about 100° C., more preferably from about 0° C. to about 70° C., mostpreferably from about 20° C. to about 50° C., particularly when acatalyst is used. When no additional catalyst is used, highertemperatures are generally advantageous. For instance, when no catalystis used and the aromatic compound is an aniline, temperatures arepreferably at least about 40° C., more preferably from about 40° C. toabout 200° C., most preferably from about 50° C. to about 150° C. Atthese temperatures, reaction times are preferably at least about 1 hour,more preferably from about 1 to about 8 hours, most preferably fromabout 3 to about 7 hours. The pressure is not critical, but convenientlyranges from about 0.1 to several hundreds of atmospheres, morepreferably from about 1 to about 50, most preferably from about 1 toabout 200 atmospheres (100-20,000 kPa). It is generally desirable to runthe reaction with less active compounds at the higher limits of theindicated ranges and the more active compounds at the lower limits ofthe indicated temperature and pressure ranges.

By controlling reaction temperatures, one can achieve substitution ofone chlorine on the dichloro compound with an aromatic compound, leavinga remaining chlorine atom unreacted. For instance, when an excess ofaniline is reacted with 9,9-dichlorofluorene at a temperature of about60° C., an exotherm to about 110° C. is observed, which exothermcorresponds to formation of 9-aminophenyl-9-chlorofluorene. Continuedheating at about 130° C. results in further alkylation to form9,9-bis(aminophenyl)fluorene. When isolation of a mono-substitutedcompound is desired, the reaction is advantageously run in a non-solventfor a compound or adduct that binds hydrochloric acid produced in themono substitution. For instance, when the aromatic compound is ananiline, the hydrochloride of the aniline forms; therefore, when thereaction is run in a non-solvent for the aniline hydrochloride, such asmonochlorobenzene, dichlorobenzene, toluene, or xylene, the anilinehydrochloride precipitates, removing the hydrochloride which is believedto otherwise act as catalyst for the substitution of the remainingchlorine atom by a second molecule of aromatic compound. It is observedthat after precipitation of the aniline hydrochloride, even additionalheating does not result in formation of the disubstituted product, e.g.bis(aminophenyl)fluorene. The mono-substituted product thus obtained isuseful for instance in reactions with aromatic compounds different fromthat used to prepare the mono-substituted product; for instance,9-aminophenyl-9-chlorofluorene is reactive with aromatic compounds suchas phenol under conditions discussed herein to produce disubstitutedcompounds such as 9-aminophenyl-9-(hydroxyphenyl)fluorene.

Although the reaction is autocatalytic because the HCl produced by thereaction is an effective catalyst, any acid catalyst, advantageously HClor any other hydrogen halide, may be added to the aromatic compound as acatalyst for the reaction, particularly as a catalyst for thethermodynamically favored (generally the para, para substitutedaromatic) product. Use of a catalyst permits reaction at temperatureslower than would be effective without a catalyst. The temperaturesdepend on the reactivity of the aromatic compound with the dichlorocompound; for instance in reactions with 9,9-dichlorofluorene, withoutcatalyst, phenol will react at about 0° C., aniline at 25° C. andtoluene at about 70° C. The catalyst is preferably added before theaddition of the dichloro compound to the aromatic compound becauseaddition of the acid catalyst is more useful before the concentration ofHCl produced in the reaction has reached a desired catalyticconcentration. For instance, while the reaction of aniline with9,9-dichlorofluorene at temperatures of more than about 20° C. does notrequire a catalyst, reaction of 9,9-dichlorofluorene with phenolpreferably involves a catalyst to proceed at atmospheric pressure andtemperatures of less than about -20° C. That catalyst, however, ispreferably a protic acid such as a hydrogen halide (preferably used atpressures greater than atmospheric pressure), or methanesulfonic (MSA),sulfuric, toluenesulfonic, hydroxybenzenesulfonic,trifluoromethanesulfonic, acetic, haloacetic, oxalic acid or mixturesthereof, at atmospheric pressure. By way of contrast, reaction of9,9-dichlorofluorene with hydrocarbons such as benzocyclobutane andtoluene preferably involve a Lewis acid catalyst, preferably AlCl₃ --CH₃NO₂, SbCl₅, FeCl₃, ZnCl₂, and more preferably ferric chloride or SbCl₅in the case of benzocyclobutane to allow reaction to occur at less thanabout 60° C. Anisole reacts with 9,9-dichloro without catalysts at 80°C., and at room temperature to 40° C. with Lewis Acid catalysts such asZnCl₂ or FeCl₃. Where, such as in the case of benzocyclobutane, the HClproduced can have a detrimental effect on the organic substrate, it isadvantageous to sparge the HCl from the reaction with an inert gas suchas nitrogen. When a hydrogen halide is used, it is advantageous toconduct the reaction under a pressure greater than atmospheric by theuse of a hydrogen halide, e.g. hydrogen chloride. The pressure of thehydrogen halide may vary from about 1 to about 1000 atmospheres,preferably from about 10 to about 100 atmospheres.

Catalyst concentration affects the distribution of isomers in a product.For instance, in the case of the reaction of phenol with9,9-dichlorofluorene, methanesulfonic acid (MSA) is an effectivecatalyst in concentrations of from about 1 percent to about 1000 percentbased on the dichloro compound, but at the lower concentrations of fromabout 1 percent to about 10 percent, the ortho, para- isomer ofbis(hydroxyphenyl)fluorene is formed along with the para, para- isomer.When the para-, para- isomer is preferred, the concentration of MSA ispreferably from about 15 percent to 1000 percent, more preferably fromabout 20 percent to about 100 percent based on the dichloro compound. Ingeneral, at atmospheric pressure and at temperatures of from about 0° toabout 170°, and for a time sufficient to isomerize the product to thethermodynamically favored isomer, increasing the concentration of MSAfrom about 1 percent to about 1000 percent, increases the concentrationof the para-, para- isomer relative to the concentration of ortho-,para- isomer of bis(hydroxyphenyl)fluorene. Similar effects are found inother alkylations of the dichloro compounds. Similarly, when HCl orother hydrogen halide is the catalyst, increasing the pressure of thehydrogen halide from atmospheric pressure to about 100 atmospheres(10,000 kPa) also increases the concentration of the thermodynamicallyfavored para, para-, isomer relative to the concentration of the ortho,para-, isomer of bis(hydroxyphenyl)fluorene. Acid can be used toisomerize less thermodynamically favored products to morethermodynamically favored products during and/or after reaction of thedichloro compounds with the aromatic compounds.

Methods of recovering product alkylated aromatic compounds from reactionmixtures are within the skill in the art. Conveniently, when there islittle excess aromatic compound remaining in the reaction mixture, acrystallization solvent is added to the reaction mixture to precipitateproduct. Advantageously, when excess reactant aromatic compound ispresent, it is removed by means within the skill in the art before acrystallization solvent is added to precipitate the product. Convenientcrystallization solvents include hydrocarbons such as pentane andhexane, aromatic hydrocarbons such as toluene and ethylbenzene;chlorinated aliphatics such as chloroform and carbon tetrachloride;ketones such as acetone and methyl ethyl ketone; and esters such asdiethyl carbonate and mixtures of these solvents. In the case of aminederivatives such as 9,9-bis(aminophenyl)fluorene, basic solutions suchas, advantageously aqueous, solutions of sodium hydroxide or sodiumbicarbonates are useful crystallization solvents. Crystallization isadvantageously enhanced by cooling of the reaction mixture before orafter addition of the crystallization solvent. Cooling alone issometimes sufficient to cause precipitation of product without additionof crystallization solvent. Before crystallization, hydrogen chloride,if present, is optionally, but preferably, removed by means within theskill in the art such as distillation. The precipitate in each case isadvantageously washed with a non-solvent therefor to remove remainingreactants.

Avoiding addition of water or other material which would result in anadditional waste to dispose is advantageous; therefore, methods ofrecovery which avoid using water to wash or otherwise isolate theproduct are of particular interest. Such methods include use of hydrogenhalides, preferably hydrogen chloride, as acid because it can be removedby such means as vaporization at reasonable temperatures without a waterwash which is generally advantageous to remove such acids as sulfuricacid and methanesulfonic acids. Solid acids such as clay and polymeracids are also removable without water washing. When approximatelystoichiometric amounts of dichloro compound and aromatic compound arereacted, especially to produce 9,9-bisarylfluorenes such as9,9-bis(hydroxyphenyl)fluorene at temperatures less than about 40° C. insuch solvents as methylene chloride, ethylbenzene, toluene, cumene,carbon tetrachloride, hexane, heptane, or other alkanes, the productprecipitates without addition of other materials; thus, theseconditions, too, are preferred for avoiding unnecessary waste disposal.The precipitate is recovered by means such as filtration and,optionally, recrystallization. Use of carbon tetrachloride as solvent inthe reaction of an excess of such aromatic compounds as phenol with suchdichloro compounds as9,9-dichlorofluorene results in a precipitateidentified as an 1:1:1 adduct of product: carbon tetrachloride: aromaticcompound which can be recovered by such means as filtration, washingwith a non-solvent for the product such as methylene chloride, a ketoneor other chlorinated solvents to remove the aromatic compound and carbontetrachloride or heating to remove carbon tetrachloride with washing toremove aromatic compound and, optionally, recrystallization from asuitable solvent, such as those suitable for washing.

In the alkylation of the dichloro compounds, isomers of the alkylationproduct are formed. For instance the reaction of phenol with9,9-dichlorofluorene, both ortho, para- and para, para-isomers of thebis(hydroxyphenyl)fluorene are formed. Analogous ortho, para- and para,para- isomers of alkylation products of other dichloro compounds arealso formed. Conversion of ortho, para- isomers to para, para- isomersis advantageous and can be accomplished by increased time in contactwith an acid such as the acid catalyst which is optionally used in thereaction of the dichloro compound with the aromatic compound, an ionexchange resin, or a hydrogen halide, e.g. liquified HCl, preferably anacid which is easily removed such as a polymeric acid (including ionexchange resin) or an acid that is easily vaporized such as a hydrogenhalide or the acid present in the reaction mixture, removal of whichwould not add additional steps to the overall process. Frequently, thereare also products representing the addition products of the dichlorocompound with one mole of the aromatic compound and with product diarylcompound. Such byproducts are conveniently reacted with additionaldichloro compound and/or additional aromatic compound to convert theminto the desired product. Conveniently, these conversions of byproductsincluding ortho, para- product is accomplished by removal of the desired(para, para-) product and addition of additional aromatic compoundand/or dichloro compound to the remaining reaction mixture; preferablythe aromatic compound is added to the mixture including the byproducts,the mixture is heated (with additional acid if needed) to rearrange theisomers, then additional dichloro compound is used. In a continuousprocess or a process having sequential batches, advantageously a recycleprocess is used in which additional aromatic compound, additionaldichloro compound and, optionally, additional acid are added to aninitial reaction mixture, then desired product is removed as additionalbyproduct mixture is added.

The process of the invention facilitates the preparation of suchcompounds as 9,9-bis(4-hydroxyphenyl)xanthene,9,9-bis(3,4-diaminophenyl)fluorene, 9,9-bis(4-carboxyphenyl)fluorene,9,9-bis(4-acetylphenyl)fluorene,9,9,10,10-tetrakis(4-hydroxyphenyl)-9,10-dihydroanthracene,10,10-bis(4-hydroxyphenyl)anthrone, 9,9-bis(methylphenyl)fluorene,9,9-bis(4-methoxyphenyl)fluorene,1,1'-(9H-fluoren-9-ylidenedi-4,1-phenylene)bismaleimide,spiro[9H-fluorene-9,9'-[9H]-xanthene]-3',6'-diol,spiro[9H-fluorene-9,9'-[9H]-xanthene]-2',7'-diol, and the likepreviously available from ketones.

The process of the invention also facilitates preparing a number ofnovel compounds including 9,9-bis(4-ethylphenyl)fluorene,9,9-bis(4-ethenylphenyl)fluorene, 9,9-bis(4-ethynylphenyl)fluorene,9,9-bis(3,4-dimethylphenyl)fluorene,9,9-bis(2,3-dimethylphenyl)fluorene,9-(3,4-dimethylphenyl)-9-(2,3-dimethylphenyl)fluorene,9,9-bis(3-amino-4-hydroxyphenyl)fluorene,9,9-bis(4-amino-3-hydroxyphenyl)fluorene,9-(3-amino-4-hydroxyphenyl)-9-(4-amino-3-hydroxyphenyl)fluorene,9,9-bis(1,3-isobenzofurandion-4-yl)fluorene,9,9-bis(1,3-isobenzofurandion-5-yl)fluorene,9-(1,3-isobenzofurandion-4-yl)-9-(1,3-isobenzofurandion-5-yl)fluorene,9,9-bis (benzocyclobutanyl)fluorene, 9,9-bis(4-halophenyl)fluorene,9,9-bis(dicarboxyphenyl)fluorene, 9,9-bis(dihydroxyphenyl)fluorene,9,9-bis(dimethylphenyl)fluorene,spiro[9H-fluorene-9,9'-[9H]carbazine]-3',6'-diol,spiro[9H-fluorene-9,9'-[9H]carbazine]-3',6'-diamine,spiro[9H-fluorene-9,9'-[9H]carbazine]-2',7'diamine,spiro[9H-fluorene-9,9'-[9H]xanthene]-2',7'-dicarboxylic acid,spiro[9H-fluorene-9,9'-[9H]xanthene]-3',6'-diamine,2',7'-diacetylspiro[9H-fluorene-9,9'-[9H]xanthene],spiro[9H-fluorene-9,13'-[13H]-6-oxapentacene]-2',10'-diol,spiro[9H-fluorene-9,13'-[13H]-6-oxapentacene]-3',9'-diol,3',6'-diaminospiro[9H-fluorene-9,9'-thiaxanthene]-10',10'-dioxide,spiro[9H-fluorene-9,9'[9H,10H]-dihydroanthracene]-2',7'-bismaleimide,10-oxo-spiro[9H-fluorene-9,9'[9H,10H]-dihydroanthracene]-3',6'-diamine,2',7'-dimethylspiro[9H-fluorene-9,9'-[9H]xanthene],2',7'-dicyanospiro[9H-fluorene-9,9'-[9H]xanthene],2',7'-diformylspiro[9H-fluorene-9,9'-[9H]xanthene],2,7-diamino-3,6-dihydroxy-9,9'-spirobifluorene,2,7-diamino-3,6-dimethyl-9,9'-spirobifluorene,spiro[9H-fluorene-9,9'[9H,10H]-dihydroanthracene]-2',7'-diamine,2',3',6',7'-tetraaminospiro[9H-fluorene-9,9'-thiaxanthene]-10',10'-dioxide,spiro[9H-fluorene-9,9'[9H]xanthene]-2',3',6,7'-tetraamine,2,3,6,7-tetraamino-9,9'-spirobifluorene,2,7-diamino-9,9'-spirobifluorene-3,6-dithiol,2,7-bis(1-methyl-1-(4-hydroxyphenyl)ethyl)spiro[xanthene-9,9'-fluorene],2,7-bis(4-hydroxyphenyl)spiro[xanthene-9,9'-fluorene],1,3,6,8,10,10-hexamethylspiro[dihydroanthracene-9,9'-fluorene]-2,7-diol,1,3,6,8-tetrabromo-10,10-dimethylspiro[dihydroanthracene-9,9'-fluorene]-2,7-diol,1,3,6,8-tetramethylspiro[dihydroanthracene-9,9'-fluorene]-2,7-diol,spiro[9H-fluorene-9,9'-[9H]xanthene]-3',6'-dicarboxylic acid,spiro[9H-fluorene-9,9'-[9H]xanthene]-2',7'-dicarbonyl chloride,spiro[9H-fluorene-9,9'-[9H]xanthene]-3',6'-dicarbonyl chloride,3',6'-dimethyl-spiro[9H-fluorene-9,9'-[9H]xanthene],2',7'-diisopropylspiro[9H-fluorene-9,9'-[9H]xanthene],3',6'-diisopropylspiro[9H-fluorene-9,9'-[9H]xanthene],2',3',6',7'-tetramethylspiro[9H-fluorene-9,9'-[9H]xanthene],spiro[9H-fluorene-9,9'-[9H]xanthene]-2',3',6',7'-tetracarboxylic acid,spiro[9H-fluorene-9,9'-[9H]xanthene]-2',3',6',7'-tetracarboxylic aciddianydride, e.g. prepared from 9,9-dichlorofluorene reacted withethylbenzene; styrene; ethylbenzene; 1,2-dimethylbenzene; o-aminophenol, phthalic anhydride, benzocyclobutane, halobenzene (e.g. bromo-,chloro-, iodo- or fluoro-benzene), phthalic acid, dimethylbenzene,catechol, hydroquinone, 3-aminophenol, p-phenylenediamine,m-phenylenediamine, 4-hydroxybenzoic acid, 4-aminophenol,4-hydroxyacetophenone, naphthalenediol, 2,7-naphthalenediol,3,3'-diaminodiphenylsulfone,1,1'-(methylenedi-4,1-phenylene)bismaleimide, 4,4'-diaminobenzophenone,p-cresol, 4-cyanophenol, 4-hydroxybenzaldehyde,4,4'-diamino-3,3'-dihydroxybiphenyl, o-tolidine, methylenedianiline,3,3',4,4'-tetraaminodiphenylsulfone, 3,3',4,4'-tetraaminodiphenyletheror 3,4-diaminophenol, 3,3',4,4'-tetraaminobiphenyl,4,4'-diaminobiphenyl-3,3'-dithiol, bisphenol A, biphenol, tetramethylbisphenol A, tetrabromobisphenol A, tetramethyl bisphenol F, m- andp-cresol, 3,4-dimethyl phenol. 3- and 4-isopropylphenol, respectively.The compounds are useful as monomers in polymers such as polyesters,polycarbonates, epoxy resins, polyamides, polyimides, polybenzoxazoles,polybenzimidazoles, benzocyclobutane polymers, polybenzthiazoles,polyquinoxalines, and as intermediates for preparing monomers. Forinstance 9,9-bis(4-ethylphenyl)fluorene is useful to prepare9,9-bis(4-ethenylphenyl)fluorene by reactions analogous to those used toprepare styrene from ethylbenzene, and9,9-bis(3,4-dimethylphenyl)fluorene is useful to prepare9,9-bis(1,3-isobenzofurandion-5-yl)fluorene by reactions analogous tothose used to prepare phthalic anhydride from xylene. The polymers areprepared by means within the skill in the art. Additionally, the processof the invention wherein mono-substitution of the gem-dichloro compoundis achieved is particularly useful to prepare such aniline derivativesas 9-(4-aminophenyl)-9-chlorofluorene, and the alkyl derivatives thereofincluding the N-alkyl and ring-substituted derivatives such as9-(4-(N-methylaminophenyl))-9-chlorofluorene,9-(4-amino-3-methylphenyl)-9-chlorofluorene,9-(4-amino-3-ethylphenyl)-9-chlorofluorene,9-(4-amino-3-chlorophenyl)-9-chlorofluorene,9-(4-amino-4-methylphenyl)-9-chlorofluorene,9-(4-amino-2-ethylphenyl)-9-chlorofluorene,9-(4-amino-2-chlorophenyl)-9-chlorofluorene, and mixtures thereof. Suchcompounds are particularly useful for further alkylation to formcompounds having mixed aromatic substituents replacing the chlorines ofthe dichloro compounds.

While products of the invention are generally useful in formingcondensation polymers when they contain at least two reactive functionalgroups (e.g. hydroxyl, amine, sulfide, acid, acid halide, anhydride, oraldhehyde groups) or in addition polymers when they contain at least onecarbon to carbon unsaturation, they can also be converted to additionalcompounds having useful functional groups. For instance phenol- and/oramine- containing products, especially phenol- and/or amine- containingderivatives of 9,9-dichlorofluorene are useful for conversion into epoxyresins by means within the skill in the art such as those described in"Epoxy Resins, Chemistry and Technology" C. A. May, Yoshio Tanaka,Marcel Dekker, Inc., NY (1973) and "Handbook of Epoxy Resins" H. Lee, K.Neville, McGraw Hill, N.Y. (1967). Similarly, the phenol-containingproducts are useful for conversion into cyanate resins by means withinthe skill in the art such as those disclosed in Angew. Chem. Int'l Ed.6, 206 (1967), E. Grigat and R. P utter; U.S. Pat. No. 4,110,364 (1978)M. Gaku, K. Suzuki, K. Nahamichi; U.S. Pat. No. 4,060,541 (1977) RudolfSunderman; U.S. Pat. No. 3,994,949 (1976) Karl-Heinrich Meyer, ClausBurkhardt, Ludwig Bottenbruch; U.S. Pat. No. 4,046,796 (1977) (GuntherRottloff, Rudolf Sundermann, Ernest Grigat, Rolf P utter); and U.S. Pat.No. 4,028,393 (1977) (Gunther Rottloff, Rudolf Sundermann, ErnestGrigat, Rolf P utter). The phenol-containing compounds are also usefulas agents for partial advancement or hardening of epoxide-containingcompounds. The amino-containing products are also useful as curingagents for epoxide-containing compounds.

The following examples are given to illustrate, but not limit theinvention. In the examples, all parts, ratios and percentages are byweight unless specified otherwise. Examples of the invention (Ex.) aredesignated numerically, while comparative samples (C.S.) are designatedalphabetically.

EXAMPLE 1 Preparation of 9,9-Dichlorofluorene from Fluorene

The reactor is a 500 mL 3-neck round bottomed flask equipped with amagnetic stir bar, nitrogen purge and thermometer. The reactor isflushed with nitrogen, and a solution of fluorene (6.00 g, 0.036 mole)and carbon tetrachloride (CCl₄) (669.48 g, 4.35 mole, 420 mL) is chargedto the reactor followed by NaOH (50 percent solution in water, 6.00 g,0.075 mole, 4.0 mL, 3.00 g dry weight). The stirrer is started and thespeed adjusted to 500 RPM (revolutions per minute). The mixture isstirred with a subsurface nitrogen sparge. The temperature of thereaction solution is 28° C. The catalyst, tetrabutylammonium hydroxide(40 percent solution in water, 1.9 g, 0.0029 mole, 1.9 mL), is added atonce.

The reaction is followed by gas chromatography (GC) on a GC(commercially available from Varian Associates under the tradedesignation Varian 3700 equipped with a 15 meter by 0.53 mm Megabore(Trademark of J&W Scientific) capillary column coated with a 1 micronfilm of polydimethylsiloxane commercially available from J&W Scientificunder the trade designation DB-1 as the stationary phase and a flameionization detector (FID)(commercially available from Varian Associatesunder the trade designation Varian 3700) with conditions of 250° C. atthe injector, 350° C. at the detector, 130° C. of the column for thefirst minute then programmed to rise 3° per minute to 160° C. and tohold that temperature for one minute. The reaction mixture is sampledafter 20 minutes and analyzed by GC which shows that the reactionmixture contains 18.46 percent fluorene, 81.54 percent9,9-dichlorofluorene. No other product is evident. The reaction issampled and analyzed periodically over the next three hours. Afterstirring overnight no fluorene remains according to the GC analysis;results are shown in Table 1. Stirring is stopped, the phases areallowed to separate, and the aqueous phase is removed from the reactor.The reaction mixture is filtered through alumina and the CCl₄ is removedon a rotary evaporator leaving 8.40 g of light yellow crystals, 99percent of theory. NMR and GC-mass spectral analysis of this materialshows it to be identical with that of a known sample of9,9-dichlorofluorene.

                  TABLE 1                                                         ______________________________________                                        CHLORINATION OF FLUORENE                                                      BY CARBON TETRACHLORIDE via                                                   PHASE TRANSFER CATALYSIS                                                                      9,9-        2,7-                                                     FLU-     DICHLORO-   DICHLORO-                                         TIME   ORENE    FLUORENE    FLUORENE  ClC.sub.14 *                            Minutes                                                                              Percent  percent     percent   percent                                 ______________________________________                                        0.00   100.00   0.00        0.00      0.00                                    20.00  18.46    81.54       0.00      0.00                                    40.00  13.92    86.09       0.00      0.00                                    60.00  10.51    89.50       0.00      0.00                                    120.00 8.62     91.39       0.00      0.00                                    180.00 4.56     95.46       0.00      0.00                                    ______________________________________                                         *Cl--C14 is a chlorofourteen carbon compound found in the product of          photochlorination of fluorene.                                           

The data in Table 1 shows that chlorination of fluorene by the processof the invention leads to 9,9-dichlorofluorene and not2,7-dichlorofluorene or the C₁ -C₁₄ compounds detected inphotochlorination of fluorene. The product is also observed to have amass spectrum corresponding to that of a known sample of9,9-dichlorofluorene with base peak at 199 atomic mass units (AMU) andparent ion at 234 AMU. The nuclear magnetic resonance (NMR) spectrum ofthe product is also consistent with that of a known sample of9,9-dichlorofluorene with peaks at 7.81-7.84 ppm (2H), 7.59-7.63 ppm(2H), 7.37-7.47 ppm (4H) relative to TMS (tetramethylsilane) in CDCl₃solution. The C¹³ NMR shows peaks at 146.69, 136.48, 130.67, 129.041.124.60, 120.14, 82.93 relative to tetramethylsilane.

COMPARATIVE SAMPLE A:

Reaction Carried Out as Described by Reeves et al.

The reactor is a 500 mL 3-neck round-bottomed flask equipped with amagnetic stir bar, nitrogen purge and thermometer. The reactor isflushed with nitrogen, and a solution of fluorene (6.00 g, 0.036 mole)and carbon tetrachloride (669.48 g, 4.35 mole, 420 mL) is charged to thereactor followed by NaOH (50 percent solution in water, 6.00 g, 0.075mole, 4.0 mL, 3.00 g dry weight). The stirrer is started and the speedadjusted to 500 rpm. The mixture is stirred with a subsurface nitrogensparge. The temperature of the reaction solution is 28° C. The catalyst,tetrabutylammonium bromide (0.93 g, 0.0029 mole), is added at once.

The reaction followed by gas chromatography (GC) as in Example 1. Thereaction mixture is sampled after 40 minutes and analysis shows 98.17percent fluorene, 1.83 percent 9,9-dichlorofluorene. The reaction issampled and analyzed periodically over the next thirty six hours. Afterthree hours, only 10.29 percent of the fluorene has been converted to9,9-dichlorofluorene compared to 95.46 percent in the previous example(Example 1). At thirty six hours, 15.16 percent of the fluorene remainsunconverted in the reaction mixture. This data shows thattetrabutylammonium bromide is not as effective a catalyst for thisreaction as is tetrabutylammonium hydroxide.

EXAMPLE 2 Use of Less than an Equivalent of Sodium Hydroxide in theChlorination of Fluorene

The reactor is a 12 inch (30.48 cm) section of 2 inch (5.08 cm) insidediameter pipe made from fluorocarbon polymer commercially available fromE.I. du Pont de Nemours & Co. under the trade designation Teflon PFAwhich is swaged to a 0.5 inch (1.27 cm) tee at the lower and upper ends.To the bottom-most leg of the lower tee is joined a stopcock which canbe used to drain the reactor's contents. To the other leg of this tee isattached the suction inlet of a pump (a magnetically driven centrifugalpump commercially available from March Manufacturing Inc. under thetrade designation March model, MDX-MT3 rated at 28.39 liters/minute atzero head). The outlet of the pump is plumbed to a heat exchangerthrough which the reaction mixture passes and which, in turn, isconnected to the top-most leg of the upper tee on the reactor. The otherleg on the upper tee is used as a port to charge reactants to and ventpurge gas from the reactor. A nitrogen sparge is provided at the inletof the heat exchanger. This design results in continuously impinging theorganic phase at a high velocity into the aqueous phase, achieving goodinterfacial contact. A thermocouple is provided at the discharge port ofthe pump for measuring the temperature of the reaction.

The reactor is flushed with nitrogen. Then a solution of fluorene (16.62g, 0.1000 mole) and carbon tetrachloride (149.60 g, 0.9726 mole, 93.85mL) is charged to the reactor followed by NaOH (30 percent solution inwater, 1.33 g, 0.010 mole, 1.00 mL, 0.40 g dry weight). The pump isstarted and the temperature adjusted to 30° C. The catalyst,tetrabutylammonium hydroxide (40 percent solution in water, 1.28 g,0.0020 mole, 1.28 mL), is added at once. The mixture is circulated witha subsurface nitrogen sparge. The temperature of the reaction solutionis 30° C.

The reaction is followed by gas chromatography (GC) by the procedure ofExample 1. Analysis after 60 minutes shows 15.46 percent fluorene, 84.09percent 9,9-dichlorofluorene.

This result shows that less than an equivalent of sodium hydroxide iseffective in achieving chlorination by the process of the invention.

EXAMPLE 3 Use of Benzyltrimethylammonium Hydroxide as Catalyst in theChlorination of Fluorene

The reactor described in Example 2 is flushed with nitrogen, and asolution of fluorene (49.87 g, 0.3000 mole) and carbon tetrachloride(448.79 g, 2.9177 mole, 281.55 mL) is charged to the reactor followed byNaOH (30 percent solution in water, 4.00 g, 0.030 mole, 3.00 mL, 1.20 gdry weight). The pump is started and the temperature adjusted to 30° C.The catalyst, benzyltrimethylammonium hydroxide (40 percent solution inwater, 2.82 g, 0.0060 mole, 2.66 mL) is added at once. The mixture iscirculated with a subsurface nitrogen sparge. The temperature of thereaction solution is 30° C. The reaction is followed by gaschromatography as in Example 1. After 60 minutes analysis shows 84.34percent fluorene, 14.20 percent 9,9-dichlorofluorene.

This example shows that benzyltrimethyl ammonium hydroxide is aneffective catalyst for this reaction.

EXAMPLE 4 Use of a Ten Percent Concentration of Sodium Hydroxide inChlorination of Fluorene

The reactor is a 1000 mL cylinder 4 inches in diameter (100 mm) by 5.5inches high (140 mm) equipped with a 2 inch (50 mm) diameter turbineimpeller driven by a vertical shaft. Stirring rate is measured by atachometer. Temperature is controlled by a 10 foot (3.048 m) by 0.25inch (0.635 cm) external diameter coil immersed in the reaction mediumthrough which coolant is pumped maintained at a constant temperature bya circulating refrigerated/heated bath.

The temperature is measured by a thermocouple inside a thermowell whichruns the entire depth of the reactor. The reactor is also equipped witha nitrogen inlet which is used to maintain a nitrogen atmosphere abovethe reaction solution. The entire apparatus is constructed offluorocarbon resin commercially available from E.I. du Pont de Nemours &Co. under the trade designation Teflon PFA.

The reactor is flushed with nitrogen. Then a solution of fluorene (14.96g, 0.090 mole) and carbon tetrachloride (134.64 g, 0.8753 mole, 84.47mL) is charged to the reactor followed by NaOH (10 percent solution inwater, 359.99 g, 0.90 mole, 324.32 mL, 36.00 g dry weight). The stirreris started and the speed adjusted to 3000 rpm. The coolant is admittedto the coils, and the temperature of the reaction solution is adjustedto 30° C. The catalyst, tetrabutylammonium hydroxide (40 percentsolution in water, 1.14 g, 0.0018 mole, 1.16 mL), is added at once. Thereaction mixture is sampled after 1 minute and analyzed by GC accordingto the method described in Example 1; it shows 94.89 percent fluorene,4.50 percent 9,9-dichlorofluorene and 0.25 percent 9-fluorenone. After15 minutes, analysis shows 94.26 percent fluorene, 4.56 percent9,9-dichlorofluorene and 0.30 percent 9-fluorenone. After an additionalthree hours, analysis shows 88.78 percent fluorene, 8.52 percent9,9-dichlorofluorene and 0.76 percent 9-fluorenone.

This example shows that even 10 percent sodium hydroxide is effective inthis reaction.

EXAMPLE 5 Use of Twenty Percent Sodium Hydroxide in the Chlorination ofFluorene

The reactor described in Example 4 is flushed with nitrogen. A solutionof fluorene (25.56 g, 0.1538 mole) and carbon tetrachloride (230.08 g,1.4958 mole, 144.34 mL) is charged to the reactor followed by NaOH (20percent solution in water, 307.59 g, 1.5380 mole, 252.13 mL, 61.52 g dryweight). The stirrer is started, and the speed adjusted to 3000 rpm. Thecoolant is admitted to the coils and the temperature of the reactionsolution is adjusted to 30° C. The catalyst, tetrabutylammoniumhydroxide (40 percent solution in water, 1.97 g, 0.0031 mole, 1.98 mL)is added at once. After 1 minute, analysis by the procedure of Example 1shows 39.65 percent fluorene, 60.04 percent 9,9-dichlorofluorene, and0.32 percent 9-fluorenone. After 15 minutes, analysis shows 1.44 percentfluorene, 98.21 percent 9,9-dichlorofluorene and 0.34 percent9-fluorenone. After a three hour reaction time analysis shows 0.97percent fluorene, 98.66 percent 9,9-dichlorofluorene and 0.37 percent9-fluorenone. This result indicates that twenty percent aqueous sodiumhydroxide is effective.

EXAMPLE 6 Use of Thirty Percent Sodium Hydroxide in the Chlorination ofFluorene

The procedure of Example 5 is repeated except that a solution offluorene (33.24 g, 0.200 mole) and carbon tetrachloride (299.20 g, 1.94mole, 187.20 mL) is charged to the reactor followed by NaOH (30 percentsolution in water, 266.66 g, 2.00 mole, 200.50 mL, 80.00 g dry weight)and the catalyst is tetrabutylammonium hydroxide (40 percent solution inwater, 2.54 g, 0.0040 mole, 2.57 mL). After 1 minute, analysis shows thereaction mixture contains 18.14 percent fluorene, 81.34 percent9,9-dichlorofluorene, and 0.51 percent 9-fluorenone. After 15 minutes,analysis shows 1.41 percent fluorene, 98.39 percent 9,9-dichlorofluoreneand 0.21 percent 9-fluorenone. After an additional one hour, 45 minutes,analysis shows 0.52 percent fluorene, 98.66 percent 9,9-dichlorofluoreneand 0.56 percent 9-fluorenone.

This example shows that 30 percent sodium hydroxide is effective in theprocess of the invention.

EXAMPLE 7 Use of 40 percent Sodium Hydroxide in Chlorination of Fluorene

The procedure of Example 5 is repeated except that a solution offluorene (33.24 g, 0.200 mole) and carbon tetrachloride (299.20 g, 1.94mole, 187.20 mL) is charged to the reactor followed by NaOH (40 percentsolution in water, 203.64 g, 2.00 mole, 139.86 mL, 80.00 g dry weight)and the catalyst is tetrabutylammonium hydroxide (40 percent solution inwater, 2.54 g, 0.0040 mole, 2.57 mL). After 1 minute, analysis showsthat the reaction mixture now contains 17.22 percent fluorene, 81.50percent 9,9-dichlorofluorene, and 1.10 percent 9-fluorenone. After 15minutes, analysis shows 0.95 percent fluorene, 98.69 percent9,9-dichlorofluorene and 0.35 percent 9-fluorenone. After an additionalone hour, 45 minutes, analysis shows 0.01 percent fluorene, 99.07percent 9,9-dichlorofluorene and 0.92 percent 9-fluorenone.

This example shows that 40 percent sodium hydroxide is effective in thisreaction.

EXAMPLE 8 Use of Fifty Percent Sodium Hydroxide in Chlorination ofFluorene

The procedure of Example 5 is repeated except that a solution offluorene (33.24 g, 0.200 mole) and carbon tetrachloride (299.20 g, 1.94mole, 187.20 mL) is charged to the reactor followed by NaOH (50 percentsolution in water, 160.00 g, 2.00 mole, 106.67 mL, 80.00 g dry weight)and the catalyst is tetrabutylammonium hydroxide (40 percent solution inwater, 2.54 g, 0.0040 mole, 2.57 mL). After 1 minute, analysis shows6.58 percent fluorene, 92.38 percent 9,9-dichlorofluorene, and 1.03percent 9-fluorenone. After 15 minutes, analysis shows 0.92 percentfluorene, 98.59 percent 9,9-dichlorofluorene and 0.49 percent9-fluorenone. After an additional one hour, 45 minutes, analysis shows0.01 percent fluorene, 92.13 percent 9,9-dichlorofluorene and 7.86percent 9-fluorenone.

This example shows that 50 percent sodium hydroxide is effective in thisreaction.

EXAMPLE 9 Use of Methylene Chloride as an Alternative Solvent with aStoichiometric amount of CCl₄.

The reactor described in Example 4 except with a baffle affixed to theimmersed coil is flushed with nitrogen, and a solution of fluorene(47.47 g, 0.2856 mole), methylene chloride (142.40 g, 1.6767 mole,107.47 mL) and carbon tetrachloride (87.85 g, 0.5711 mole, 55.11 mL) ischarged to the reactor followed by NaOH (30 percent solution in water,380.75 g, 2.8556 mole, 286.28 mL, 114.23 g dry weight). The stirrer isstarted and the speed adjusted to 3000 rpm. The coolant is admitted tothe coils and the temperature of the reaction solution is adjusted to30° C. The catalyst, tetrabutylammonium hydroxide (40 percent solutionin water, 3.633 g, 0.0057 mole, 3.67 mL), is added at once.

Analysis by the procedure of Example 1 at one minute shows 3.35 percentfluorene, 95.76 percent 9,9-dichlorofluorene, and 0.89 percent9-fluorenone. After 15 minutes, analysis shows 0.78 percent fluorene,99.05 percent 9,9-dichlorofluorene and 0.17 percent 9-fluorenone. Afteran additional hour, analysis shows 0.00 percent fluorene, 99.02 percent9,9-dichlorofluorene and 0.65 percent 9-fluorenone.

This example shows that good results are obtained using alternativesolvents such as methylene chloride with only a stoichiometric amount ofCCl₄.

EXAMPLE 10 Use of Cumene as an Alternative Solvent with a Stoichiometricamount of CCl₄.

The procedure of Example 9 is repeated except that a solution offluorene (33.24 g, 0.200 mole) cumene (188.38 g, 1.5672 mole, 218.04 mL)and carbon tetrachloride (61.53 g, 0.400 mole, 38.60 mL) is charged tothe reactor followed by NaOH (50 percent solution in water, 160.0 g,2.00 mole, 103.9 mL, 80.00 g dry weight); and the catalyst istetrabutylammonium hydroxide (40 percent solution in water, 2.59 g,0.004 mole, 2.57 mL). After 1 minute, analysis shows 0.92 percentfluorene, 97.05 percent 9,9-dichlorofluorene, and 2.03 percent9-fluorenone. After 15 minutes, analysis shows 0.92 percent fluorene,97.27 percent 9,9-dichlorofluorene and 1.81 percent 9-fluorenone. Thisdata shows that the reaction is essentially complete within one minuteunder these conditions.

This example shows that good results are obtained using alternativesolvents such as cumene with only a stoichiometric amount of CCl₄.

EXAMPLE 11 Use of Ethylbenzene as an Alternative Solvent with aStoichiometric amount of CCl₄.

The procedure of Example 9 is repeated except that a solution offluorene (33.24 g, 0.200 mole), ethylbenzene (188.38 g, 1.7743 mole,217.28 mL), and carbon tetrachloride (61.53 g, 0.400 mole, 38.60 mL) ischarged to the reactor followed by NaOH (50 percent solution in water,160.0 g, 2.00 mole, 103.9 mL, 80.00 g dry weight); and the catalyst istetrabutylammonium hydroxide (40 percent solution in water, 2.59 g,0.004 mole, 2.57 mL). After 1 minute, analysis shows 1.23 percentfluorene, 97.78 percent 9,9-dichlorofluorene, and 0.59 percent9-fluorenone. After 15 minutes, analysis shows 1.29 percent fluorene,97.84 percent 9,9-dichlorofluorene and 0.87 percent 9-fluorenone.

This example shows that good results are obtained using alternativesolvents such as ethylbenzene with only a stoichiometric amount of CCl₄.

EXAMPLE 12 Use of Ethylbenzene as an Alternative Solvent with aStoichiometric amount of CCl₄ with 30 percent Sodium Hydroxide.

The procedure of Example 9 is repeated except that a solution offluorene (33.24 g, 0.200 mole) ethylbenzene (188.38 g, 1.7 743 mole,217.28 mL) and carbon tetrachloride (61.53 g, 0.400 mole, 38.60 mL) ischarged to the reactor followed by NaOH (30 percent solution in water,266.67 g , 2.00 mole, 200.5 mL, 80.00 g dry weight); and the catalyst istetrabutylammonium hydroxide (40 percent solution in water, 2.59 g,0.004 mole, 2.57 mL). The reaction mixture is sampled after 1 minute andperiodically thereafter for the next 30 minutes and analyzed by GCaccording to the procedure in Example 1. GC analysis at one minute shows25.65 percent fluorene, 74.35 percent 9,9-dichlorofluorene, and 0.0percent 9-fluorenone. GC analysis at 15 minutes shows 1.28 percentfluorene, 98.72 percent 9,9-dichlorofluorene, and 0.0 percent9-fluorenone. GC analysis at 30 minutes shows 1.19 percent fluorene,98.81 percent 9,9-dichlorofluorene, and 0.0 percent 9-fluorenone.

This result shows that ethylbenzene is effective as a solvent when usedwith a stoichiometric amount of carbon tetrachloride with 30 percentsodium hydroxide.

EXAMPLE 13 Continuous Preparation of 9,9-dichlorofluorene

This reaction is carried out in a reactor constructed from a 2 inch(5.08 cm) diameter pipe of fluorocarbon resin commercially availablefrom E.I. du Pont de Nemours & Co. under the trade designation TeflonPFA. The reactor contains 6 stirred sections each 1.75 inches (4.45 cm)long separated by horizontal spacers 0.25 inch (0.64 cm) thick which areperforated with eight 0.25 inch (0.64 cm) diameter holes which allowcommunication between the stages. Centered within each stage is animpeller mounted on a vertical drive shaft constructed of type 316stainless steel which is 0.375 inches (0.954 cm) tall, by 0.625 inches(1.651 cm) in diameter. An air driven motor drives the drive shaft at aconstant speed of 1500 rpm. Each stirred section is approximately 100 mLin volume. The top of the reactor is equipped with ports for theintroduction of nitrogen and venting the same such that an inertatmosphere can be maintained during the course of the reaction. Theupper-most stirred section or stage contains a port for the introductionof reactants and a thermowell for measuring the temperature of thereactor's contents. There are additional thermowells in stage four fromthe top and just below the sixth stage. Below the sixth stage from thetop there is a twelve inch (30.48 cm) long section which is unstirredand acts as a quiet zone so that the organic and aqueous phases candisengage or phase separate. At the bottom of this reactor is a teewhich is connected to a bottom drain on one leg so that the entirecontents of the reactor can be removed, and to an overflow tube on theother leg which can be adjusted to control the liquid level in thereactor. The product solution can be continuously drawn off thisoverflow at a rate equivalent to that which the feed solution isintroduced to the first stage of the reactor.

The reactor is purged with nitrogen and then charged with a volume ofcarbon tetrachloride (400 mL) such that its level just comes to thebottom of the sixth stage. NaOH solution (50 percent by weight, 12.0moles, 480 g dry weight, 960 g solution weight, 627.45 mL) is thencharged to the reactor, which fills all six of the stirred zones. Thestirrer is started and its speed is adjusted to 1500 rpm. Fluorene (3.0moles, 498.66 g) dissolved in carbon tetrachloride (64.84 moles, 9973.20g, 6256.71 mL) is fed into the first reactor stage through a meteringpump at a rate of 19 mL/min. At the same time, tetrabutylammoniumhydroxide (0.03 moles, 7.78 g dry weight, 19.46 g as 40 percent aqueoussolution) is fed through a separate metering pump into the first reactorstage at a rate of 0.05 mL/min. The product solution is collected at theoverflow and analyzed by gas chromatography (GC) on a gas chromatographcommercially available from Varian Associates under the tradedesignation Varian 3400 GC equipped with a 30 meter by 0.53 mm Megabore(Trademark of J&W Scientific) capillary column coated with a 1 micronfilm of polytrifluoropropyl-co-dimethylsiloxane commercially availablefrom J&W Scientific under the trade designation DB-210 as the stationaryphase and a flame ionization detector (FID) commercially available fromVarian Associates under the trade designation Varian 3400.

When fluorene is no longer detected in the effluent stream the productis fed to a wash column which is identical in design to the reactorcolumn. The product solution is fed to the first stirred stage at a rateof 10 mL/min and water is fed at the sixth stirred stage at a rate of 20mL/min. The organic solution containing the 9,9-dichlorofluorene iscollected at the overflow of the wash column and then passed through acolumn of molecular sieves (4A size, commercially available from LindeDivision, Union Carbide Industrial Gasses Inc.) which lowers the watercontent of the stream as measured by Karl-Fisher titration from 211 ppmto 11.4 ppm. The total product solution collected in this fashionamounts to 12,004 g which is 5.8 weight percent 9,9-dichlorofluorene and0.05 weight percent fluorenone.

EXAMPLE 14 Large Scale Preparation of Bis(hydroxyphenyl)fluorene

Fluorene (800 lb, 363.63 kg) is dissolved in methylene chloride (2722lb, 1237.27 kg) in a tank. Then an amount of carbon tetrachloride (CCl₄)stoichiometric with the fluorene (1488 lb, 676.36 kg) is added to theresulting solution and mixed thoroughly using a retreated bladeagitator. The resulting solution is charged via nitrogen pad into a 1000gallon (3785 liter) glass lined reactor containing (4963 lb, 256 kg) ofa 30 weight percent aqueous solution of sodium hydroxide (NaOH) which isat a temperature of 25° C. The reactor is maintained at a temperature of25° C. by a flow of a 50 weight percent aqueous solution of ethyleneglycol through a steel jacket around the reactor. The reactor is purgedwith nitrogen. After all of the fluorene solution is charged to thereactor and phase separation occurs (about 10-15 minutes), agitation isbegun. Either the aqueous phase or the organic phase can be a continuousphase.

While the temperature is maintained at 25° C. to avoid catalystdeterioration, (12.5 lb, 5.68 kg) of tetra-n-butylammonium hydroxide inaqueous solution (40 percent) is fed to the reactor at a rate of 2.84kg/hr over a period of 2 hours. Agitation and cooling are continued forone hour, after which agitation is stopped. This is to assure that allof fluorene has been reacted. Reaction of all fluorene is confirmed byGC analysis of the reaction mixture, then the phases are allowed toseparate with the organic phase on the bottom of the reactor.

The organic phase is removed at a rate of 1500 lb/hr (681.81 kg/hr)using a centrifugal pump until a small rag layer (where phases areincompletely separated) remains. The organic phase is then washed with1200 lb/hr (545 kg/hr) portions of water three times with separation ofwater from the organic phase each time. The organic phase is found tocontain about 23 weight percent dichlorofluorene (DCF) in methylenechloride with some CCl₄ and chloroform present. That phase is thenstored and mixed with subsequent batches of essentially the samecomposition prepared by the same process. Optionally, the phase could beused immediately to prepare bis-(hydroxyphenyl)fluorene. Repeating thesynthesis of DCF offers an opportunity to reuse the NaOH solution.Optionally, the organic phase could be dried using a molecular sievecolumn to remove water.

After a desired number of batches of DCF are produced, the NaOH solutionis pumped from the reactor to the wash section. The sodium hydroxidesolution is then treated with sufficient HCl (hydrochloric acid) toneutralize the NaOH.

The reactor and associated piping are flushed with methylene chloride.

Fifty five gal (208 1) of molten phenol at 50° C. is transferred to areactor using a nitrogen pad. During transfer, the phenol is maintainedunder a nitrogen atmosphere and weighed such that 232 kg (25 molepercent excess based on 9,9-dichlorofluorene) are transferred into the1000 gal. (3785 1) reactor which is also purged with nitrogen.Methanesulfonic acid (MSA) (93 lbs, 42.2 kg) is added to the reactor asthe catalyst for the phenolation process. For the first batch, thereactor does not contain the recycled material. After the first batch,the reactor content contains the recycled material which consists ofchloroform, methylene chloride, p,p-BHPF, o,p-BHPF, 3,2-fluorene-phenoladducts, MSA and phenol. The entire content of the reactor is circulatedaround the reactor using the pump at the bottom of the reactor and theagitator inside the reactor.

A 1207.27 kg portion of the DCF in methylene chloride is added to therecirculation loop of the reactor containing phenol at a rate of 603.63kg/hr, over a period of 2 hours while the reactor is maintained at 15°C. by cooling in the jacket of the reactor. The pressure remainsatmospheric. Precipitation of product p,p-bis(hydroxyphenyl)fluorene(p,p-BHPF) is noted after about half of the DCF is added.

The addition of DCF is completed after 2 hours, precipitation of productp,p-bis(hydroxyphenyl)fluorene (p,p-BHPF) is noted after about half ofthe DCF is added, but the contents of the reactor are allowed to digest(remain at the same temperature with stirring) over the period of 1 hourat 40° C. Then the reaction mixture is allowed to cool down to 10° C.over a 1 hour period. HCl produced during the first two hours of thereaction is vented into a scrubber containing 500 1 of 15 weight percentaqueous NaOH. Heat is removed from the scrubber using an external heatexchanger to cool the circulated sodium hydroxide. After 95 percent ofthe HCl is removed by venting it to the scrubber, then sufficientnitrogen is introduced from the bottom of the reactor to remove HCl.When removal of HCl is complete as determined by the pH of the solutionnot being acidic, the remaining contents of the reactor (hereinafter,reaction mixture) are transferred to a holding tank using a pump. Thereaction mixture is a slurry.

After the entire contents of the reactor have been transferred (130 gal,492.05 1), the slurry of crystalline product in reaction mixture istransferred to a pressure filter unit commercially available fromRosenmund, Inc. where a pressure of 15 psi (103.41 kPa) is applied usingnitrogen pressure. The amount transferred is controlled by weighing theslurry feed tank before and after transfer using a commercial weightcell.

During transfer to the filter unit, a drain valve is closed; whentransfer is complete and no malfunction of the filter is noted, thevalve is opened and a pressure of 35 psig, (241.29 kPa) of nitrogen isapplied such that a filtrate containing methylene chloride, excessphenol, carbon tetrachloride, chloroform, p,p-BHPF; o,p-BHPF andphenol-fluorene adducts is collected in a check tank.

The filtrate is transferred from the check tank to a batch distillationunit to remove a mixture of chloroform and methylene chloride, whichmixture is suitable for recycle to wash the filter cake. Before thedistillation starts, 232.25 kg phenol with 42.27 kg methanesulfonic acidare added to the batch distillation pot. Then the distillation ofchloroform and methylene chloride is started. After all of thechloroform and all of the methylene chloride have been removed, theremaining filtrate (about 15 percent by weight) is transferred to awaste storage tank, the rest of the mixture is maintained at atemperature of 70° C. and a pressure of 103.41 kPa under nitrogen for aperiod of one hour to isomerize the phenol-fluorene adducts and o,p-BHPFto p,p-BHPF.

A filter cake of BHPF forms on the filter and is washed using therecovered methylene chloride/chloroform mixture by closing the drainvalve, charging the mixture to the filter apparatus at a rate of 10gal/min (37.85 1/min) until a total of 100 gal (378.5 1) is charged,opening the valve and applying a pressure of 35 psig (241.29 kPa) ofnitrogen. The mixture is pushed through the filter cake and collectedthen recycled to be used with the isomerization mixture. The recycledmethylene chloride (MeCl₂)/chloroform solution is sent back to the batchdistillation pot. The washing step above is repeated two more times:first with the recycled MeCl₂ solution, and then with fresh MeCl₂solution; only a trace of MSA remains in the filter cake.

The wet filter cake is found to contain about 45 weight percentmethylene chloride and is suitable for use in a process in whichmethylene chloride is suitabler or can be washed with water to displacemost of the methylene chloride by making a slurry of it with water oneor more times. The water preferably contains about 1 percent Na₂ CO₃ andis at about 70° C., then the filter cake is preferably washed with purewater at 70° C. to remove all residual MSA in the wet cake. Optionally,and alternatively, the filter cake is dried, first by using 30 psig (207kPa) steam to strip MeCl₂ from the cake then using a pressure of 35 psi(241.29 kPa) nitrogen at a temperature of at least 50° C. blowingthrough the filter cake to dry the water from the cake. The pressedpressure filter has a mechanical agitator arm to stir up the cake andbreak up the clump to aid in the drying process.

The filter cake is optionally slurried back in water solution before thedrying step to transfer out of the filter apparatus or is optionallydried and transferred out as a solid.

The BHPF is produced in about 80 percent yield based on DCF and has amelting point of 223°-225° C. and the purity of 99 percent as determinedby HPLC analysis when prepared as described, without the isomerizationstep. With the recycle of the adducts and isomers back to theisomerization steps, the overall yield of the process is 95 percent.

Those skilled in the art will recognize that a number of variations onthese processes are within the scope of the invention. For instance,phenol may be added in solution (for instance, in methylene chloride) oras a solid. DCF can be added to phenol or other phenolic solution in thephenolation reaction in the form of a solid. The product p,p-BHPF can berecrystallized in methylene chloride. The chlorination reaction can becarried out in a continuous reactor instead of a batch reactor. Thephenolation reaction can be carried out in a continuous reactor. ProductBHPF can be recrystallized either in addition to or alternative tofiltration; alternatively, the BHPF can be used without drying if usedin a system where methylene chloride is an acceptable solvent.Similarly, solid separation of the reaction product slurry is optionaland can be accomplished by any means within the skill in the art such asbasket centrifuge, solid bowl centrifuge, other forms of solidseparation and the like. A filter cake can also be washed in a slurrywash and/or displacement wash using fresh or recycled methylene chlorideor other non-solvent; a slurry wash would involve stirring the filtercake with the non-solvent until a slurry is formed, and removal of saidnon-solvent, for instance by filtration or other solid separationtechnique.

EXAMPLE 15 Preparation of 9,9-Bis(4-methylphenyl)fluorene; Alkylation ofDCF onto Toluene using FeCl₃ as Catalyst

Dichlorofluorene (10.0 g, 0.042 mole) (DCF) prepared as in Example 13and ferric chloride (0.1 g, 0.0006 mole) are weighed into a 50 mL2-necked flask fitted with a stirbar, nitrogen inlet, and thermometer.Toluene (50 mL) is added and the mixture is stirred and heated with aheating mantle. The mixture rapidly becomes dark red, and begins toevolve HCl. At a temperature of 40° C., the solution vigorously evolvesHCl. Analysis by GC (using a gas chromatograph commercially availablefrom Varian Associates under the trade designation Model 3700, with a 30meter column coated with a 1 micron layer of polydimethylsiloxanecommercially available from J&W Scientific under the trade designationDB-1) at this point shows almost all of the DCF has reacted, and severalheavy products are formed.

The mixture is then heated at 50° C. for 1hour, after which, thesolution is black in color. Analysis of the mixture by GC shows all theDCF has been reacted. The mixture is worked up by washing with water andthen diluting the mixture (solution) with pentane, which causes theprecipitation of most of the product as a tan powder. This powder isfiltered from the solution. The remaining mother liquor is thenevaporated, and the resulting solid is slurried in pentane and filtered.The remaining mother liquor is evaporated to give an oily yellow solid.Weight of precipitated product is: first crop, 6.92 g; second crop, 2.64g ; total, 9.56 g (65 percent of theoretical); weight of yellow solid,2.19 (15 percent of theoretical weight).

The H-NMR is consistent with a sample of 9,9-bis(methylphenyl)fluorene(MPF) having peaks relative to tetramethylsilane (TMS) at δ2.1-2.5 (m,6H, CH₃), 6.6-7.9 (m, 16H). C-13 NMR: δ151.63, 145.41, 143.17, 140.15,138.44, 136.09, 129.15, 128.89, 128.33, 127.95, 127.79, 127.41, 126.12,125.42, 120.21, 119.69, 65.42, (p,p isomer, quaternary C) 64.90 (o,pisomer, quaternary C), 21.59 (CH₃), 21.08 (CH₃).

As determined by gas chromatography/mass spectroscopy (GCMS) the productmixture is: 77.3 percent bis(4-methylphenyl)fluorene, 16.4 percent(4-methylphenyl)(2-methylphenyl)fluorene, 6.2 percentbis(2-methylphenyl)fluorene. Primary peaks on GCMS for each compoundare: (in atomic mass units, AMU, with percentage of height of base(largest) peak at 100 percent in parenthesis after the AMU) inparenthesis after the AMU: for bis(4-methylphenyl)fluorene: 347(27.3);346(100.0); 331(24.6); 255(17.3); 239(13.7); 65(14.0); for(4-methylphenyl)-(2-methylphenyl)fluorene: 347(28.2); 346(100.0);331(16.9); 255(18.5); 253(11.3); 65(12.37); and forbis(2-methylphenyl)fluorene: 347(27.5); 346(100.0); 331(21.5);255(18.0); 65(14.5).

EXAMPLE 16 Preparation of 9,9-Bis(4-methoxyphenyl)fluorene; Alkylationof DCF onto Anisole using Sulfonic Acid Polymer Catalyst

Dichlorofluorene (0.5 g, 0.002 mole) is weighed into a 50 mL 2-neckedflask fitted with a stirbar, nitrogen inlet, and septum. Anisole (1.08g, 0.01 mole) is added, and a GC (using a gas chromatograph commerciallyavailable from Varian Associates under the trade designation Model 3700,with a 30 meter column coated with a 1 micron layer ofpolydimethylsiloxane commercially available from J&W Scientific underthe trade designation DB-1) is taken of the resulting mixture as astandard. Activated Dow Fluorinated Sulfonic Acid (DFSA) pelletsprepared by the process disclosed in U.S. Pat. No. 4,791,081 andavailable from The Dow Chemical Company under the trade designation XU40036.01, heated at 170° C. for 24 hours under vacuum (<10 mm Hg) toactivate, then stored under nitrogen, are added to the mixture. Then themixture is heated in a water bath. At a temperature of 50° C., thepellets begin to turn purple. When the mixture has reached 60° C., thesolution has taken on a purple cast. The mixture is heated to 80° C.over 2 hours, at which time the solution is a yellow color, and thecolor of the DFSA beads is a light reddish color. Analysis of themixture by GC shows that all the DCF has been reacted. The solution isdecanted, and the excess anisole is removed under vacuum. The product, athick yellow oil, is analyzed by H and C-13 NMR (Nuclear MagneticResource). The pattern observed in the aromatic region of the H-NMR isconsistent with para substitution of the anisole. The C-13 shows 12carbons for the main product (a small amount of a byproduct is seen atthe base of these peaks) which is the number of distinct carbon signalsthat would be predicted for the desired product. H-NMR: delta 3.79 (s,6H, OCH₃), 7.89-6.86 (m, 16H), all from a standard of tetramethylsilane.C-13 NMR: delta 158.3, 151.9, 140.0, 138.2, 129.2, 127.6, 127.2, 126.1,120.4, 113.6, 64.2 (quaternary C), 55.2 (OCH₃) from a standard oftetramethylsilane.

EXAMPLE 17 Polymerization of DCF with Diphenylcarbonate (DPC) usingTiCl₃ Catalyst

DCF (9,9-Dichlorofluorene, 1.18 g, 0.005 mole) and DPC(diphenylcarbonate, 1.07 g, 0.005 mole) are weighed into a 25 mLtwo-necked flask fitted with a stirrer, heating mantle, and thermometer.Chloroform (4 mL) is added, followed by a catalytic amount of TiCl₃(0.03 g, 0.0002 mole) and the mixture is stirred and heated to 60° C.over a period of 4 hours. After 30 minutes, the mixture has turned adark red color, and is evolving HCl. After stirring for about 4 hoursfrom the addition of the catalyst, the mixture solidifies and formsbrown paste. The paste is dissolved in dichloromethane (except someinsoluble portions), and then diluted with acetone. This causes theprecipitation of the product as a brown powder which is filtered fromthe yellow solution. The melting point of the powder is >280° C.

EXAMPLE 18 Polymerization of DCF with Diphenyloxide (DPO) using ZnCl₂ asCatalyst

DCF (9,9-Dichlorofluorene, 5.88 g, 0.025 mole) is weighed into a 150 mLresin kettle along with diphenyl oxide (DPO) (4.28 g, 0.0251 mole) andchloroform (10 mL). The kettle is fitted with a condenser and mechanicalstirrer, and a starting GC (using a gas chromatograph commerciallyavailable from Varian Associates under the trade designation Model 3700,with a 30 meter column coated with a 1 micron layer ofpolydimethylsiloxane commercially available from J&W Scientific underthe trade designation DB-1) is taken as a reference. The mixture isstirred and heated in a water bath (40°-50° C.). A small amount of ZnCl₂is added (about 0.02 g) and the mixture is stirred and heated at 50-70°C. After 30 minutes of heating the mixture has turned a dark greencolor, and is evolving HCl. Shortly thereafter, a thick solid paste isdeposited on the walls of the kettle. This thick paste does not dissolvewhen 100 mL chloroform is added. The paste is triturated with acetone,which causes the solid to turn off-white in color. The off-white solidis filtered from the acetone and dried. The acetone is evaporated toyield a greenish semi-solid. The off-white polymer weighs 5 grams (60percent of theoretical) and has a melting point (under a pressure of68,000 kPa) of 250° C. The polymer is pressed into a thin, clear film at250° C. and about 10,000 psig (700 kg/cm²). The film is brittleindicating low molecular weight. The Tg of the polymer is measured at179° C. (onset) by DSC (Differential Scanning Calorimetry).

EXAMPLE 19 Reaction of 9,9-Dichlorofluorene with Phenol to Prepare9,9-Bis(hydroxyphenyl)fluorene

This reaction is carried out in a reactor constructed from fluorocarbonresin commercially available from E.I. du Pont de Nemours & Co. underthe trade designation TEFLON PFA in the form of 2 inch (5.08 cm)diameter pipe 12 inches (30.48 cm) in length. At the top of the reactoris a 1/2 inch (1.27 cm) diameter port containing a ball valve throughwhich phenol is added to the reactor. Also attached to the top of thereactor is a nitrogen purge line as well as a vent line (attached to asodium hydroxide scrubber). Attached two inches (5.08 cm) above thebottom of the reactor is (1) a thermowell and (2) an inlet line whichserves as a point of HCl injection and/or sampling of the reactionmixture. Contained in the reactor is a star-shaped magnetic stir barwhich, when acted upon by an external magnetic stir plate, providesagitation to the reaction mixture. Approximately six inches (15.24 cm)from the bottom of the reactor is attached a feed line through which asolution of 9,9-dichlorofluorene (DCF) (or other dichloro compound) ispassed into the reactor from an external holding tank. The reactor iswrapped with an electric heating tape attached to a variable voltagecontroller which serves to regulate the temperature of the reactionmixture.

Molten (60° C.) phenol (94.1 g, 1.0 mole) is poured into the reactor andthe ball valve closed. While the phenol is stirred, the variable voltagecontroller is adjusted to maintain the phenol temperature between 40°and 45° C. A sample of 63.9 grams of a solution of DCF in carbontetrachloride and containing 6.45 g (0.027 mole) of DCF, are placed inthe DCF holding tank. When reactor temperature is stable, anhydrous HClis passed slowly into the phenol until reactor pressure is approximately15 psig (pounds per square inch gauge) (102 kPag). At this point, HCladdition is ceased and nitrogen pressure is used to force the DCFsolution from the holding tank into the reactor. Total time for additionof the DCF solution is approximately 30 seconds. Reactor pressure ismaintained at approximately 20 psig (136 kPag) by adjusting flow throughthe vent line with a needle valve. After 2 hours reaction time, thereactor contents are removed and quantitatively analyzed by reversephase liquid chromatography (HPLC). Selectivity to p,p-BHPF is found tobe 70 percent.

EXAMPLE 20 Effect of Phenol: DCF Molar Ratio

The procedure of EXAMPLE 19 is repeated except that 509.7 g of the DCFsolution (0.23 mole DCF) are added to the reactor and reactor pressureis 90 psig (612 kPag). After 2 hours reaction time, the reactor contentsare removed and treated with 167 g isopropyl alcohol, thenquantitatively analyzed by reverse phase liquid chromatography (HPLC).Selectivity to p,p-BHPF is 54 percent.

EXAMPLE 21 Effect of Using Methanesulfonic Acid (MSA) as Catalyst

The procedure of EXAMPLE 20 is repeated except 100 g (1.06 mole) ofphenol and 5 g methanesulfonic acid (MSA) are placed in the reactor and267.8 g of a DCF/carbon tetrachloride solution (7.9 percentweight/weight in DCF) are added to the reactor and no HCl is passed intothe reactor. After approximately 2 hours reaction time, the temperatureof the reaction mixture is increased from 40°-45° C. to approximately70° C. and maintained at these conditions for another 17 hours. Thereaction mixture is quantitatively analyzed by reverse phase liquidchromatography (HPLC). Selectivity to p,p-BHPF is 86 percent.

EXAMPLE 22 USE of MSA at Atmospheric Pressure

A sample of 25.0 g (0.266 mole) phenol and 7.5 g methanesulfonic acid(MSA) are stirred in a 3-necked 250 mL round-bottom flask equipped witha Dewar condenser containing dry ice. A solution of DCF is prepared byadding 25.03 g (0.106 mole) DCF to a mixture containing 39.9 g methylenedichloride and 20.1 g chloroform. When the temperature of the phenol/MSAmixture is approximately 30° C., the DCF solution is added to the flask,via dropping funnel, over a 20 minute period. After 2 1/2 hours reactiontime, the reaction mixture is heated with a heating mantle to atemperature of 38°-40° C. and maintained at this temperature for 3hours. The solution is then allowed to cool overnight. The reactionmixture is filtered and the filter cake washed with methylene chlorideto yield a white solid which, after drying to constant weight at 60° C.,yields 20.8 g of a white solid. HPLC analysis indicates the white solidto be 96 percent p,p-BHPF by peak area. Quantitative analysis of thefiltrate by HPLC reveals 10.5 g p,p-BHPF to be dissolved in thefiltrate. Overall selectivity to p,p-BHPF is 84 percent.

EXAMPLE 23 Effect of Water

The procedure of EXAMPLE 22 is repeated except a) 22.0 g (0.234 mole)phenol is used, b) the methylene chloride is saturated with deionizedwater prior to preparing the DCF solution and c) reaction temperature is25° C. After 2 hours selectivity to p,p-BHPF is 62 percent.

EXAMPLE 24 Effect of Sulfuric Acid

A sample of 40.0 g (0.425 mole) phenol is added to a 250 mL Erlenmeyerflask containing a magnetic stir bar and fitted with a thermometer. Withstirring, 5.6 g (0.06 mole) 96 percent sulfuric acid and 0.1 mL (1.15millimole) β-mercaptopropionic acid are added to the phenol. A sample(25.0 g 0.106 mole) DCF is added as a solid to the phenol/acid mixtureover a 20 minute period during which the temperature of the reactionmixture never exceeds 50° C. After 2 hours reaction, the reactionmixture is dissolved in isopropyl alcohol and quantitatively analyzed byHPLC. Selectivity going to p,p-BHPF is 70 percent.

EXAMPLE 25 Effect of Temperature

A sample of hot phenol. (249.2 g, 2.65 mole, at a temperature of 70° C.)is placed in a 1 liter, 3-necked round-bottomed flask fitted with athermometer, distillation arm and a dropping funnel. While the contentsare stirred and heated to approximately 100° C., anhydrous HCl isbubbled into the phenol. A sample of (250 mL) of a DCF/CCl₄ solutionwhich contains 0.089 mole of DCF (as determined by HPLC analysis) ischarged to the dropping funnel. When the temperature of the phenol/HClsolution has stabilized at 98° to 100° C., the DCF solution is slowlydripped into the phenol/HCl solution. As the DCF solution is added, adistillate is collected from the reaction mixture. When all of the DCFhas been added, the HCl flow is discontinued and the contents of theflask are allowed to cool. After 15 hours total reaction time, thereaction mixture is quantitatively analyzed by HPLC. Selectivity is 66percent going to p,p-BHPF.

EXAMPLE 26 Use of Trifluoromethanesulfonic (Triflic) Acid as Catalyst

The procedure of EXAMPLE 25 is repeated except that (a) 0.5 mL oftriflic acid is added to the flask in lieu of HCl, and (b) 750 mL of theDCF/CCl₄ solution are placed in the dropping funnel. Selectivity is 50percent relative to p,p-BHPF.

EXAMPLE 27 Use of Trifluoromethanesulfonic Acid as Catalyst

To a 100 mL 3-necked flask equipped with a thermometer, magnetic stirbar, condenser and a nitrogen inlet through which a positive nitrogensweep is maintained, 32.4 g of phenol is added. The temperature isadjusted to 41° C. and nitrogen is swept through the system for tenminutes. At this point, triflic acid (0.1 mL) is added to the flask.Solid crystals of 9,9-dichlorofluorene, obtained by evaporating thesolvent from the DCF/CCl₄ solution used in EXAMPLE 13, are added overthe next hour. The temperature of the reaction mixture is maintained at40° C. for four more hours and then sampled for HPLC analysis whichshows a 91 percent yield.

EXAMPLE 28 Use of Ethyl Acetate as Solvent

The procedure of EXAMPLE 18 is repeated except a mixture of 91 g ethylacetate and 100 g (1.06 mole) phenol are added to the reactor, 2) 24 g(0.102 mole) DCF are dissolved in 123 g ethyl acetate and placed in theDCF holding tank, 3) the DCF solution is added over a 5 minute period,4) HCl addition is continued during DCF addition, reaction temperatureis allowed to vary from room temperature to 41° C. and 5) reactorpressure is not controlled (never exceeds 22 psig (149.6 kPag)). After16 hours reaction time, the reaction mixture is collected andquantitatively analyzed by HPLC. Selectivity to p,p-BHPF is 53 percent.

EXAMPLE 29 Use of Isopropanol as Solvent

A sample of 100 g isopropyl alcohol and 208 g (2.21 mole) phenol arecombined and saturated with anhydrous HCl in a 500 mL erlenmeyer flask.A solution of 24 g (0.102 mole) DCF in 200 g carbon tetrachloride isadded to the stirred phenol/alcohol solution over a 50 minute periodduring which the reaction mixture is continuously sparged with anhydrousHCl. After 95 minutes reaction time, the reaction mixture is collectedand quantitatively analyzed by HPLC. Selectivity to p,p-BHPF is 69percent.

EXAMPLE 30 Effect of Pressure, Temperature, and Time on Selectivity

The procedure of EXAMPLE 18 is repeated except temperature is controlledat 60°-70° C. and reactor pressure is controlled at 80-90 psig (612kPag) and reaction time is 15.5 hours. Selectivity to p,p-BHPF is 85percent.

EXAMPLE 31 Use of a Recirculating Reactor

The basic reactor configuration is 1) a 2 inch (5.08 cm) diameter pipeof fluorocarbon resin commercially available from E.I. du Pont deNemours & Co. under the trade designation Teflon PFA which serves as themixing tank, 2) a heat exchanger of the same material 3) a feed tank inwhich a solution of 9,9-dichlorofluorene is stored prior to starting thephenolation reaction and 4) a pump which continually circulates thereactor contents through the heat exchanger and mixing tank.

A solution of 57 g (0.6 mole) of phenol in approximately 236 mL of CCl₄is placed in the reactor mixing tank. After the reactor is sealed, thepump is energized, and the solution is allowed to circulate through thesystem. At this point an ethylene glycol/water mixture commerciallyavailable from The Dow Chemical Company under the trade designationAmbitrol™ 50 which has been cooled to 10° C., is admitted to the heatexchanger to maintain a reactor temperature of 17° C. Upon stabilizationof the CCl₄ /phenol solution temperature, anhydrous HCl is admitted intothe headspace of the mixing tank, and reactor pressure is regulated at10 psig (68 kPag) by means of a flow meter on the vent line. A solutionof CCl₄ /9,9-dichloro fluorene (DCF) is prepared by dissolving 14.1 g(0.06 mole) of DCF in approximately 88 mL of CCl₄. The solution ischarged to the DCF feed tank and pressured to 30 psig (204 kPag) withnitrogen. A flow meter connecting the DCF feed tank to the suction ofthe circulating pump is then opened to admit the DCF/CCl₄ solution intothe reactor system at a rate of 3.1 g/minute. Samples of the reactionmixture are periodically removed via the sampling line and analyzed byreverse phase liquid chromatography (HPLC) to determine extent ofreaction and distribution of reaction products. After 23 hours reactiontime, the reaction mixture is analyzed by HPLC. p,p-BHPF comprises 44percent of all reaction products as measured by peak area.

EXAMPLE 32 Effect of Phenol Concentration and Temperature

The procedure of EXAMPLE 31 is repeated except: a) 191.3 g (2.04 mole)phenol is added to the reactor followed by 180 mL CCl₄, b) 250 mL of aDCF/CCl₄ solution containing 0,089 mole of DCF (as determined by HPLCanalysis) is charged to the DCF feed tank, c) reactor temperature iscontrolled at 64° C. After 6 hours, the reaction mixture is analyzed byHPLC; analysis shows p,p-BHPF comprises 49 percent of all reactionproducts as measured by peak area.

EXAMPLE 33 Use of Glacial Acetic Acid as Solvent

The procedure of EXAMPLE 31 is repeated except that 100 g (1.1 mole) ofphenol and 100 mL of glacial acetic acid are placed in the reactormixing tank. The reactor is sealed, the pump is energized, and thesolution is allowed to circulate through the system. At this point anethylene glycol/water mixture commercially available from The DowChemical Company under the trade designation Ambitrol™ 50, which hasbeen cooled to 25° C., is admitted to the heat exchanger to maintain areactor temperature of 30° C. Upon stabilization of the phenoltemperature, anhydrous HCl is injected into the suction of thecirculation pump until reactor pressure is 20 psig (136 kPag), at whichpoint the HCl flow is discontinued. A solution of CCl₄ /9,9-dichlorofluorene (prepared by dissolving 24 g (0.1 mole) of DCF in approximately60 mL of CCl₄ and 200 mL glacial acetic acid) is charged to the DCF feedtank and pressured to 40 psig (272 kPag) with nitrogen. A flow meterconnecting the DCF feed tank to the suction of the circulating pump isthen opened to admit the DCF/CCl₄ solution into the reactor system at arate of 5.5 g/min. The reaction mixture is analyzed by HPLC. Selectivityto p,p-BHPF is 27 percent.

EXAMPLE 34 Use of Catalyst Dissolved in DCF

A sample of 24.0 g (0.102 mole) DCF is dissolved in 88 g ethyl acetate.This solution is sparged with anhydrous HCl until 13.1 g HCl hasdissolved in the solution. A sample of 297 g (3.16 mole) molten (60° C.)phenol is placed in a 1-L Erlenmeyer flask and stirred. The ethylacetate/DCF/HCl solution is added slowly to the phenol. HPLC analysisindicates 84 percent of product peak area is that of p,p-BHPF.

EXAMPLE 35 Reverse Addition: Phenol into DCF

The procedure of EXAMPLE 34 is repeated except that the ethylacetate/DCF/HCl solution is placed in a 500 mL Erlenmeyer flask andstirred while HCl is sparged through the solution. Molten (60° C.)phenol is added to the ethyl acetate/DCF/HCl solution over a 1 hourperiod. After 4.3 hours, HPLC analysis shows p,p-BHPF to be 74 percentof the products' peak areas.

EXAMPLE 36 Use of Propylene Carbonate as Solvent

A sample of 1.1 g (0.012 mole) phenol is dissolved in 1.0 g propylenecarbonate/0.1 mL β-mercaptopropionic acid (BMPA). A solution of 1.25 g(0.0053 mole) DCF in 2 g methylene chloride/1 g chloroform is added tothe propylene carbonate/phenol/-BMPA solution. Anhydrous HCl is slowlysparged into the mixture to initiate reaction. After 1.5 hours, HPLCanalysis shows p,p-BHPF to constitute 62 percent of the products' peakareas.

EXAMPLE 37 Direct Addition of Phenol to a Chlorination Reaction toObtain p,p-BHPF

The reactor is a 1000 mL cylinder 4 inches in diameter (100 mm) by 5.5inches in height (140 mm) equipped with a 2 inch (50 mm) diameterturbine impeller driven by a vertical shaft. Stirring rate is measuredby a tachometer. Temperature is controlled by a 10 foot (3.048 m) by0.25 inch (0.635 cm) external diameter coil immersed in the reactionmedium through which coolant is pumped maintained at a constanttemperature by a circulating refrigerated/heated bath.

The temperature is measured by a thermocouple inside a thermowell whichruns the entire depth of the reactor. The reactor is also equipped witha nitrogen inlet which is used to maintain a nitrogen atmosphere abovethe reaction solution. The entire apparatus is constructed ofpolytetrafluoroethylene/copolyheptafluoropropyl trifluorovinyl ethercommercially available from E.I. du Pont de Nemours & Co. under thetrade designation Teflon PFA.

The reactor is flushed with nitrogen and a solution of fluorene (33.24g, 0.200 mole) and carbon tetrachloride (299.20 g, 1.9451 mole, 187.70mL) is charged to the reactor followed by NaOH (30 percent solution inwatery 53.33 g, 0.40 mole, 40.10 mL, 16.00 g dry weight). The stirrer isstarted, and the speed adjusted to 4000 rpm. The coolant is admitted tothe coils, and the temperature of the reaction solution is adjusted to30° C. The catalyst, tetrabutylammonium hydroxide (40 percent solutionin watery 2.59 g, 0.004 mole, 2.57 mL) is added at once. The reactionmixture is sampled after 30 minutes and analyzed by GC according to theprocedure of EXAMPLE 1; analysis shows 0.38 percent fluorene, 98.74percent 9,9-dichlorofluorene, and 0.88 percent 9-fluorenone. Phenol(41.41 g, 0.44 mole, 38.70 mL) in 42.46 mL of CCl₄ is added to thereactor and stirring is continued. After 30 minutes the reaction mixtureis sampled and analyzed by reverse phase liquid chromatography (HPLC) asin EXAMPLE 19 which shows the composition of the mixture to now be 41.70percent 9,9-bis(4-hydroxyphenyl)fluorene, 2.45 percent o,p-BHPF, 5.42percent 9-fluorenone, and 4.76 percent 9,9-dichlorofluorene.

EXAMPLE 38 Addition of Phenol as Phenolate in Aqueous Solution Directlyto the Chlorination Reaction to Obtain the pyp-BHPF

The reactor described in EXAMPLE 37 is flushed with nitrogen, and asolution of fluorene (33.24 g, 0.200 mole), ethylbenzene (188.38 g,1.7743 mole, 217.28 mL) and carbon tetrachloride (61.53 g, 0.400 mole,38.60 mL) is charged to the reactor followed by NaOH (50 percentsolution in water, 160.0 g, 2.00 mole, 103.9 mL, 80.00 g dry weight).The stirrer is started, and the speed adjusted to 3000 rpm. The coolantis admitted to the coils, and the temperature of the reaction solutionis adjusted to 30° C. The catalyst, tetrabutylammonium hydroxide (40percent solution in water, 2.59 g, 0.004 mole, 2.57 mL), is added atonce. The reaction mixture is sampled after 1 minute and periodicallythereafter for the next 30 minutes and analyzed by GC according to theprocedure used in EXAMPLE 1. The results of these analyses are shown inTable 2.

                  TABLE 2                                                         ______________________________________                                        TIME     percent      percent  percent                                        (Minutes)                                                                              Fluorene     9,9-DCF  Fluorenone                                     ______________________________________                                        0.00     99.41        0.00     0.59                                           1.00     1.23         97.78    0.99                                           2.00     1.51         97.61    0.88                                           3.00     1.45         97.76    0.78                                           4.00     1.40         97.98    0.62                                           5.00     1.54         97.75    0.71                                           10.00    1.54         97.59    0.88                                           15.00    1.29         97.84    0.87                                           20.00    1.21         97.92    0.87                                           30.00    1.15         98.10    0.75                                           ______________________________________                                    

The data in Table 2 show that the reaction is essentially completewithin one minute. GC analysis at one minute shows 1.23 percentfluorene, 97.78 percent 9,9-dichlorofluorene, and 0.59 percent9-fluorenone. After 30 minutes, phenol (37.64 g, 0.40 mole, 35.18 mL) in10.39 mL of 50 percent NaOH (0.40 mole, 16.00 g dry weight) is added tothe reactor and stirring continued. After 30 minutes analysis shows76.97 percent DCF remaining and 1.96 percent BHPF. The mixture isallowed to stir overnight; then analysis shows 100.0 percent9,9-bis(4-hydroxyphenyl)fluorene.

EXAMPLE39 Preparation of Bis(aminophenyl)fluorene

Into a two-neck round bottomed flask provided with a thermometer and acondenser are placed 9,9-dichlorofluorene (10.0 g, 0.0425 mole) andaniline (50.0 g, 0.537 mole). The resulting mixture is slowly heatedover a period of about 30 minutes to 60° C. in an oil bath with stirringusing a magnetic stirrer. A rapid reaction takes place with an exotherm(˜110° C.) and results in complete disappearance of dichlorofluorene andappearance of one product as confirmed by GC/MS (gas chromatographicmass spectrometry), showing a primary peak at 254-257 AMU,to be9-chloro-9-(aminophenyl)fluorene. Further heating at 130° C. for threehours results in complete conversion of the monoamine to the diamine.Excess aniline is flash distilled under vacuum, and the resultingresidue is washed with 5 percent sodium hydroxide, filtered, and washedwith hexane to give 14.0 g (94 percent yield) of the diamine, which isfound to be a mixture of 91 percent p,p'- and 9 percent N,p-isomers byGLC (gas liquid chromatography); m.p. 234°-235° C. The mass spectrumshows a primary peak at 348 AMU.

The diamine is recrystallized by pouring it into boiling toluene andcooling the resulting mixture to precipitate pure p,p'-isomer, m.p.234°-235° C.; NMR (¹ H and ¹³ C) data is consistent with9,9-bis(paminophenyl)fluorene structure. The ¹ H NMR of the compound ind₆ -DMSO (deutero-dimethylsulfoxide) shows peaks at δ4.90 (singlet, NH₂,2H), 6.40 (doublet, aromatic, 4H), δ6.75 (doublet, aromatic, 4H),δ7.2-7.3 (multiplet, fluorene, 6H), δ7.8-7.9 (multiplet, fluorene, 2H),all from TMS (tetramethylsilane) standard.

When the procedure is repeated except that heating at 130° C. iscontinued for a period of 7 hours rather than 3 hours, the product is 98percent p,p'- and 2 percent N,p- isomer. This data indicates thatheating converts the N,p- isomer to the p,p'- isomer.

EXAMPLE 40 Effect of Recycling Byproducts to Increase para, para-BHPF

In this example, recycle is illustrated by 5 batch reactions.

Reaction #1: To a 100 mL glass flask equipped with a thermometer,stirring paddle, and a cooling/heating glycol jacket are added 15.98grams (0.170 moles) of phenol in 8.60 grams of chloroform plus 3.07grams of methanesulfonic acid (MSA) to form a solution. This solution isstirred and kept at 24° C. To this solution are added 18.04 g (0.0768moles) of 9,9-dichlorofluorene (DCF) in 18.1 grams chloroform plus 8.4grams methylene chloride over a period of 75 minutes. After the DCF isadded, the temperature is 27° C. That temperature is maintained for 60minutes, then the solution is cooled to 10° C. which is maintained 60minutes. Crystals form and are collected on a glass filter frit andwashed with a total of 100 mL of methylene chloride and then a total of100 grams of warm water. The resulting 10.7 grams of BHPF is determinedto be 99 percent pure by HPLC analysis, and the crystals have a meltingpoint of 223°-225° C. This melting point indicates that the isomer isp,p-BHPF. The filtrate/methylene chloride wash is used for the recyclereaction below.

Reaction #2: Recycle: Eighty-four percent of the filtrate/methylenechloride wash from Reaction #1 is added back to the glass reactor usedin Reaction #1 with 7.22 grams (0.0767 moles) of phenol and 0.49 gramsof MSA. The resulting solution is heated to 70° C. which is maintainedfor one hour while most of the methylene chloride and chloroform areremoved by vacuum distillation. Then the remaining mixture is cooled to24° C. and 5 g of methylene chloride are added. Then the mixture isseeded with 0.005 g BHPF crystals to promote crystallization. After 10minutes, 8.89 grams (0.0378 moles) of DCF dissolved in a mixture of 9.0g CHCl₃ and 19 g CH₂ Cl₂ are added over a period of 108 minutes. Thetemperature is raised to 40° C. and maintained at that temperature for60 minutes, then cooled to 10° C. and maintained at that temperature forone hour. The resulting crystals are collected on a glass filter fritand washed as in Reaction #1. The resulting 13.1 grams of BHPF isdetermined to be 99 percent pure by HPLC analysis, and the crystals havea melting point of 223°-225° C. The filtrate/methylene chloride wash isused for the next recycle reaction, Reaction #3.

Reaction #3--Recycle: Eighty-five percent of the filtrate/methylenechloride wash from Reaction #2 is added back to the glass reactor usedin Reactions #1 and #2, with 8.36 grams (0.0888 moles) of phenol and0.46 grams of MSA. The resulting solution is heated to 70° C. andmaintained at that temperature for one hour while most of the methylenechloride and chloroform are removed by vacuum distillation. Then thesolution is cooled to 24° C., and 5 g of methylene chloride are added.Then the resulting mixture is seeded with 0.005 g BHPF crystals. After10 minutes, 10.23 grams (0.0435 moles) of DCF in the same solvent mix asReaction #2 are added over a period of 130 minutes. The temperature israised to 40° C. and maintained at that temperature for 60 minutes, thencooled to 10° C. and maintained at that temperature for one hour. Theresulting crystals are collected on a glass filter frit and washed as inReaction #1. The resulting 11.9 grams of BHPF is determined to be 99percent pure by HPLC analysis, and the crystals have a melting point of223°-225° C. The filtrate/methylene chloride wash is used for the nextrecycle reaction, Reaction #4.

Reaction #4--Recycle: Eighty-five percent of the filtrate/methylenechloride wash from Reaction #3 is added back to the glass reactor usedin Reactions #1 and #3 with 7.92 grams (0.0842 moles) of phenol and 0.46grams of MSA. The resulting solution is heated to 70° C. and maintainedat that temperature for one hour while most of the methylene chlorideand chloroform are removed by vacuum distillation. Then the solution iscooled to 24° C. and seeded with 0.005 g BHPF crystals. After 10minutes, 9.54 grams (0.0406 moles) of DCF in the same solvent mix usedin Reaction #2 are added over a period of 110 minutes. The temperatureis raised to 40° C. and maintained at that temperature for 60 minutes,then cooled to 10° C. and maintained at that temperature for one hour.The resulting crystals are collected on a glass filter frit and washedas in Reaction #3. The resulting 11.4 grams of BHPF is determined to be99 percent pure by HPLC analysis, and the crystals have a melting pointof 223°-225° C. The filtrate/methylene chloride wash is used for thenext recycle reaction, Reaction #5.

Reaction #5--Recycle: Eighty-five percent of the filtrate/methylenechloride wash from Reaction #4 is added back to the glass reactor usedin Reactions #1 and #4 with 7.58 grams (0.0805 moles) of phenol and 0.45grams of MSA. The resulting solution is heated to 70° C. and maintainedat that temperature for one hour while most of the methylene chlorideand chloroform are removed by vacuum distillation. Then the solution iscooled to 24° C., and 5 g of methylene chloride are added. Then themixture is seeded with 0.005 g BHPF crystals. After 10 minutes, 9.21grams (0.0392 moles) of DCF in the same solvent mix as Reaction #2 areadded over a period of 115 minutes. The temperature is raised to 40° C.and maintained at that temperature for 60 minutes, then cooled to 10° C.and maintained at that temperature for one hour. The resulting crystalsare collected on a glass filter frit and washed as in Reaction #1. Theresulting 11.0 grams of BHPF is determined to be 99 percent pure by HPLCanalysis, and the crystals have a melting point of 223°-225° C.

The results of Reactions #2-#5 shows the usefulness of a recycle processto convert the byproducts of the reaction to BHPF using MSA as thecatalyst. A steady state is produced where the conversion rate to BHPFis 95 percent. [(moles of BHPF/moles of DCF feed -15 percent, which isremoved) X 100=95 percent]

EXAMPLE 41 Recycle to form p,p-BHPF Exemplified in 3 Reactions

Reaction #41:1 To a 100 mL glass flask equipped with a thermometer,stirring paddle, and a cooling/heating glycol jacket are added 15.98grams (0.170 moles) of phenol in 8.60 grams of chloroform plus 3.07grams of methane sulfonic acid (MSA). The resulting solution is stirredand heated to 68° C. To the solution, are added 18.04 g (0.0768 moles)of dichlorofluorene (DCF) in 18.1 grams chloroform plus 38.4 gramsmethylene chloride over 60 minutes. After the DCF is added, thetemperature is kept at 68° C. and maintained at that temperature for 30minutes then slowly dropped to 45° C. over a period of 20 minutes. Thenthe solution is seeded with 0.005 g BHPF crystals. The temperature isdecreased to 10° C. while 26 grams of methylene chloride are added. Thetemperature is maintained at 10° C. for 60 minutes. The resultingcrystals are collected on a glass filter frit and washed with 100 gmethylene chloride and then with 100 g warm water. The resulting 12.9grams of BHPF are determined to be 99 percent pure by HPLC analysis, andthe crystals have a melting point of 223°-225° C. The filtrate/methylenechloride wash is used for the recycle reaction, Reaction #41:2.

Reaction #41:2--Recycle: To the glass reactor described in Reaction 41:1is added the flitrate/methylene chloride wash from Reaction #41:1 with8.12 grams (0.0863 moles) of phenol to form a solution. The solution isstirred and heated to 68° C. To the solution, are added 10.04 g (0.0427moles) of DCF in 10.0 grams chloroform plus 21.4 grams methylenechloride over 67 minutes. After the DCF is added, the temperature ismaintained at 68° C. and maintained at that temperature for 50 minutesthen slowly dropped to 45° C. Then, 5 g of methylene chloride are addedand the mixture is seeded with 0.005 g BHPF crystals. The temperature isdecreased to 10° C. while 25 grams of methylene chloride are added. Thetemperature is maintained at 10° C. and maintained at that temperaturefor 60 minutes. The resulting crystals are collected on a glass filterfrit and washed with methylene chloride and then warm water as inReaction 41:1. The resulting t0.6 grams of BHPF is determined to be 99percent pure by HPLC analysis, and the crystals have a melting point of222°-225° C. The flitrate/methylene chloride wash is used for therecycle reaction, Reaction 41:3.

Reaction #41:3--Recycle: To the glass reactor used in Reactions #41:1and #41:2 is added the flitrate/methylene chloride wash from Reaction#41:2 with 5.72 grams (0.0608 moles) of phenol to form a solution. Thissolution is stirred and heated to 68° C. and maintained at thattemperature for 90 minutes. The temperature is decreased to 30° C., then7.04 g (0.0300 moles) of DCF in 7.14 grams chloroform plus 15.1 gramsmethylene chloride are added over a period of 90 minutes. After the DCFhas been added, the temperature is lowered to 10° C. and maintained at10° C. for 60 minutes. The resulting crystals are collected on a glassfilter frit and washed with methylene chloride and then warm water as isReaction 41:1. The resulting 10.0 grams of BHPF is determined to be 99percent pure by HPLC analysis, and the crystals have a melting point of223°-225° C.

The results of Reactions #41:2-#41:3 show that conversion of byproductto BHPF takes place and that recycle is, therefore, useful.

EXAMPLE 42 Use of Tetraalkylammonium Hydroxide as Base in Chlorinationof Fluorene

The reactor used in EXAMPLE 1 is flushed with nitrogen. A solution offluorene (12.50 g, 0.0752 mole), ethylbenzene (112.50 g, 1.0596 mole,129.76 mL) and carbon tetrachloride (23.14 g, 0.150 mole, 1.451 mL) ischarged to the reactor. The stirrer is started and the speed adjusted to500 rpm. The temperature of the reaction solution is 30° C. Thecatalyst, tetrabutylammonium hydroxide (40 percent solution in water,24.39 g, 0.0376 mole, 24.15 mL) is added at once. The reaction mixtureis sampled after 5 minutes and periodically thereafter for the next 30minutes and analyzed by GC by the procedure described in EXAMPLE 1. Theresults of these analyses are shown in Table 3. The reaction isessentially complete within thirty minutes. GC analysis at five minutesshows that the reaction mixture contains 33.26 percent fluorene, and66.74 percent 9,9-dichlorofluorene. After 30 minutes GC analysis showsthat the reaction mixture contains 0.14 percent fluorene, and 99.86percent 9,9-dichlorofluorene.

                  TABLE 3                                                         ______________________________________                                        TIME     percent      percent  percent                                        (Minutes)                                                                              Fluorene     9,9-DCF  Fluorenone                                     ______________________________________                                        0.00     100.00       0.00     0.00                                           5.00     33.26        66.74    0.00                                           10.00    14.07        85.93    0.00                                           15.00    11.03        88.97    0.00                                           30.00    0.14         99.86    0.00                                           ______________________________________                                    

This example shows that organic bases like tetraalkylammonium hydroxidesare useful in chlorination processes of the invention.

EXAMPLE 43 Use of an Ion Exchange Catalyst

To a 100 mL flask is added 20 grams (0.2125 moles) of phenol plus 13grams of CCl₄ and 6.67 grams of a dried acid ion exchange resincommercially available from The Dow Chemical Company under the tradedesignation MSC-1. The flask is heated to 40° C., and 5.15 grams (0.0219moles) of DCF in 60.8 grams of CCl₄ /CHCl₃ are added over a one hourperiod. The temperature is raised to 60° C. and maintained for a periodof one hour. HPLC analysis indicates 84 percent selectivity to p,p-BHPF.

EXAMPLE 44 Use of an Acid Clay Catalyst

To a 100 mL flask is added 20 grams (0.2125 moles) of phenol plus 14grams of CCl₄ and 6.00 grams of a dried clay acid catalyst commerciallyavailable from Harshaw/Filtrol under the trade designation Filtrol-22.The flask is heated to 40° C., and 5.07 grams (0.0216 moles) of DCF in59.9 grams of CCl₄ /CHCl₃ are added over a one hour period. Thetemperature is kept at 40° C. for 20 minutes then cooled to 24° C. TheBHPF crystals are collected by filtration, leaving a filtrate, and driedat 40° C. for 16 hours under a vacuum of 28 in Hg (6.7 kPa) to give 5.7grams of product. The catalyst is washed with acetonitrile. HPLCanalysis of the acetonitrile plus the filtrate shows 1.10 grams of BHPFin the solution. Total selectivity is 90 percent to p,p-BHPF.

EXAMPLE 45 Use of a Fluorocarbon Sulfonic Acid Catalyst

To a 100 mL flask is added 18.3 grams (0.1945 mol) of phenol plus 18.5grams of CCl₄ and 10.0 grams of fluorocarbon sulfonic acid catalyst(0.139 meq/g) prepared by the process disclosed in U.S. Pat. No.4,791,081 and available from The Dow Chemical Company under the tradedesignation XU-40036.01 (DFSA). The flask is heated to 40° C. and 4.95grams (0.0210 moles) of DCF in 58.5 grams of CCl₄ /CHCl₃ are added over7.5 hours. HPLC analysis indicates 90 percent selectivity to p,p-BHPF.

EXAMPLE 46 Effect of Metals on Chlorination

The reactor is a 500 mL 3-neck round bottom flask equipped with amagnetic stir bar, nitrogen purge and thermometer. The reactor isflushed with nitrogen and a solution of fluorene (15.00 g, 0.090 mole)and carbon tetrachloride (234.89 g, 1.52 mole, 147.36 mL) is charged tothe reactor followed by NaOH (30 percent solution in water, 6.65 g,0.050 mole, 5.00 mL, 2.00 g dry weight). The stirrer is started, and thespeed adjusted to 500 rpm. The mixture is stirred with a subsurfacenitrogen sparge. The temperature of the reaction solution is 27° C. Thecatalyst, tetrabutylammonium hydroxide (40 percent solution in water,4.95 g, 0.0076 mole, 4.90 mL) is added at once. The reaction is followedby gas chromatography (GC) as in Example 1. After 5 minutes, GC analysisshows that the reaction mixture contains 74.95 percent fluorene, and25.05 percent 9,9-dichlorofluorene. The reaction is sampled and analyzedperiodically over the next several hours until no fluorene remainsaccording to the GC analysis.

This procedure is repeated with the addition of 10 g of each of themetals indicated in Table 4 to the flask before any of the otherreagents. The results are tabulated in Table 4. The 304-stainless steeland 316-stainless steel are in the form of washers whereas the othermetals are in the form of cuttings produced from drilling operations.These cuttings have much greater surface area than the washers but stillhave less inhibitory effect on the reaction than the stainless steelwashers.

                  TABLE 4                                                         ______________________________________                                        Percent 9,9-DCF FORMED IN PRESENCE OF METAL                                                           304- 316-        TI-                                  TIME   GLASS    IRON    SS*  SS*  NICKEL TANIUM                               ______________________________________                                         0.00  0.00     0.00    0.00 0.00 0.00   0.00                                  5.00  25.05    79.26   19.41                                                                              17.58                                                                              48.10  44.23                                15.00  49.44    83.00   38.31                                                                              34.70                                                                              82.67  75.29                                30.00  52.64    89.24   49.30                                                                              44.66                                                                              87.15  83.97                                60.00  77.83    92.70   60.30                                                                              54.62                                                                              91.63  92.64                                105,00 88.89    93.21   68.87                                                                              62.38                                                                              92.69  96.34                                180.00 99.95    94.13   77.48                                                                              70.18                                                                              96.34  97.98                                1020.00                                                                              100.00   94.10   77.08                                                                              69.89                                                                              96.23  97.56                                ______________________________________                                         *SS = Stainless Steel                                                    

In all cases tabulated where a metal is present, the reaction does notgo to completion even after 17 hours; whereas, the reaction in glasswith no metal present is 99.95 percent complete at three hours and allfluorene is converted at 17 hours. The large surface area of thecuttings is believed to contribute to mixing thereby resulting in higherinitial rates of reaction for the mixtures where cuttings are present.

EXAMPLE 47 Use of Methylene Chloride as Solvent in Alkylation andIsolation without Water Wash

A sample of 23.1 g (0.246 mole) phenol is placed in a 500 mL 3-neckedround bottomed flask equipped with a magnetic stir bar, thermometer anddropping funnel. A solution prepared from 25.03 g (0.107 mole) DCF and59 g methylene chloride is placed in the dropping funnel. While thephenol is still fluid (at 35° C.), drop-wise addition of the DCFsolution is started and continued over a period of 90 minutes until allthe solution has been added. Reaction temperature is maintained at roomtemperature (about 25° C.) during the course of the reaction. After 3hours total reaction time, the reaction mixture is filtered to yield asolid which, after rinsing with methylene chloride and drying toconstant weight at 60° C., weighs 20.8 g. HPLC analysis indicates thewhite solid to be greater than 95 percent p,p-BHPF by peak area.Quantitative analysis of the filtrate by HPLC indicates 3.5 g p,p-BHPFstill dissolved in the filtrate. Selectivity to p,p-BHPF is 66 percent.

EXAMPLE 48 Non-aqueous Isolation of Alkylation Product where Chloroformis Alkylation Solvent

To a 100 mL flask is added 6.2 grams (0.66 moles) of phenol plus 3.35grams of CHCl₃ (chloroform). The flask is cooled to 11° C., and 6.0grams (0.0255 moles) of DCF in 3.14 grams of CHCl₃ and 13.1 grams of CH₂Cl₂ is added within 5 seconds. The temperature is kept at 11° C. for 4hours, then resulting BHPF crystals are collected on a glass filterfrit, washed with 9 grams of CH₂ Cl₂ and dried to give 4.63 grams ofBHPF.

EXAMPLE 49 Continous Method for the Preparation of 9,9-Dichlorofluorenewith Recovery and Recycle of the Phase Transfer Catalyst and SodiumHydroxide

Part A:

To the reactor described in Example 13 which has been purged withnitrogen is charged a volume of carbon tetrachloride (400 mL) such thatits level just comes to the bottom of the sixth stage. NaOH solution (25percent by weight, 6.14 moles, 245.6 g dry weight, 983 g solutionweight, 774.0 mL) is then charged to the reactor, and fills all six ofthe stirred zones. The stirrer is started and its speed is adjusted to1500 rpm. Fluorene (0.185 moles, 30.75 g) dissolved in carbontetrachloride (2.24 moles, 344.8 g, 225.35 mL) is fed into a verticalcatalyst saturator which is a cylinder 1 inch (2.54 cm) in diameter by12 inches (30.48 cm) long containing the catalyst solution(tetrabutylammonium hydroxide (0.132 moles, 34.30 g dry weight, 85.75 gas 40 percent aqueous solution)) such that the feed solution fallsthrough the aqueous catalyst solution before entering the first reactorstage, using a metering pump at a rate of 5.5 mL/min. The productsolution is collected at the overflow and analyzed by gas chromatography(GC) according to the procedure of Example 13.

When fluorene is no longer detected in the effluent stream, the productis fed to a wash column which is identical in design to the reactorcolumn. The product solution is fed to the first stirred stage at a rateof 5.5 mL/min and water is fed at the sixth stirred stage at a rate of11.0 mL/min. The organic solution containing the 9,9-dichlorofluorene iscollected at the overflow of the wash column and then passed through acolumn of molecular sieves (4A size, commercially available from LindeDivision, Union Carbide Industrial Gasses Inc.) which lowers the watercontent of this stream as measured by Karl-Fisher titration from 208 ppmto 6.3 ppm. The total product solution collected in this fashion amountsto 1026 g which is evaporated to dryness on a rotary evaporator, leaving42.52 g of very light yellow crystals, 9,9-dichlorofluorene (97.76percent of the theoretical yield of 43.49 g).

The aqueous solution from the wash column is evaporated on the rotaryevaporator (40° C./10 mm of Hg (1.32 kPa)) leaving 33.4 g of a clear oilwhich crystallizes (long needles) on cooling (97.4 percent recovery ofthe tetrabutylammonium hydroxide charged (34.30 g dry weight)).

Recycle run #1.

The tetabutylammonium hydroxide recovered from the above reaction (33.4g, 0.129 moles) is dissolved in 57 mL water and charged to the catalystsaturator.

To the reactor which has been purged with nitrogen is charged a volumeof carbon tetrachloride (400 mL) such that its level just comes to thebottom of the sixth stage. NaOH solution (the same solution used in theprevious run (Example 49), Part A), 25 percent by weight, 6.14 moles,245.6 g dry weight, 983 g solution weight, 774.0 mL) is then charged tothe reactor, and fills all six of the stirred zones. The stirrer isstarted and its speed adjusted to 1500 rpm. Fluorene (0.185 moles, 30.75g) dissolved in carbon tetrachloride (2.24 moles, 344.8 g, 225.35 mL) isfed into the catalyst saturator containing the catalyst solution using ametering pump at a rate of 5.5 mL/min. The product solution is collectedat the overflow and washed and dried as in Part A. The total productsolution collected in this fashion amounts to 1056 g which is evaporatedto dryness on a rotary evaporator leaving 42.66 g of very light yellowcrystals, 9,9-dichlorofluorene (98.1 percent of the theoretical yield of43.49 g).

The aqueous solution from the wash column is evaporated on the rotaryevaporator (40 C/10 mm of Hg (1.32 kPa)) leaving 32.7 g of a clear oilwhich crystallizes (long needles) on cooling (98.0 percent recovery ofthe tetrabutylammonium hydroxide charged (33.40 g dry weight).

Recycle run #2.

The tetrabutylammonium hydroxide recovered from the Recycle run #1reaction (32.7 g, 0.126 moles) is dissolved in 55 mL water and chargedto the catalyst saturator.

To the reactor which has been purged with nitrogen is charged a volumeof carbon tetrachloride (400 mL) such that its level just comes to thebottom of the sixth stage. NaOH solution (the same solution used inRecycle run #1, 25 percent by weight, 6.14 moles, 245.6 g dry weight,983 g solution weight, 774.0 mL) is then charged to the reactor, andfills all six of the stirred zones. The stirrer is started and its speedadjusted to 1500 rpm. Fluorene (0.185 moles, 30.75 g) dissolved incarbon tetrachloride (2.24 moles, 344.8 g, 225.35 mL) is fed into thecatalyst saturator containing the catalyst solution using a meteringpump at a rate of 5.5 mL/min. The product solution is collected at theoverflow, washed and dried as in Part A. The total product solutioncollected in this fashion amounts to 1006 g which is evaporated todryness on the rotary evaporation leaving 42.23 g of very light yellowcrystals, 9,9-dichlorofluorene (97.1 percent of the theoretical yield of43.49 g).

The aqueous solution from the wash column is evaporated on the rotaryevaporator (40° C./10 mm (1.32 kPa)) leaving 32.5 g of a clear oil whichcrystallizes (long needles) on cooling (99.3 percent recovery of thetetrabutylammonium hydroxide charged (32.70 g dry weight).

Recycle run #3.

The tetrabutylammonium hydroxide recovered from the above reaction (32.5g, 0.125 moles) is dissolved in 55 mL water and charged to the catalystsaturator.

To the reactor which has been purged with nitrogen is charged 400 mLcarbon tetrachloride such that its level just comes to the bottom of thesixth stage. NaOH solution (the same solution used in Recycle run #2, 25percent by weight, 6.14 moles, 245.6 g dry weight, 983 g solutionweight, 774.0 mL) is then charged to the reactor, and fills all six ofthe stirred zones. The stirrer is started and its speed adjusted to 1500rpm. Fluorene (0.185 moles, 30.75 g) dissolved in carbon tetrachloride(2.24 moles, 344.8 g, 225.35 mL) is fed into the catalyst saturatorcontaining the catalyst solution using a metering pump at a rate of 5.5mL/min. The product solution is collected at the overflow and washed anddried as in Recycle run #2. The total product solution collected in thisfashion is 1046 g which is evaporated to dryness on the rotaryevaporator leaving 41.11 g of very light yellow crystals,9,9-dichlorofluorene (94.5 percent of a theoretical yield of 3.49 g).

The aqueous solution from the wash column is evaporated on the rotaryevaporation (40° C./10 mm of Hg (1.32 kPa)) leaving 30-3 g of a clearamber oil (93.2 percent recovery of the tetrabutylammonium hydroxidecharged (32.5 g dry weight )).

These results show that both the phase transfer catalyst and base can berecovered and/or reused (recycled) in the practice of the invention.

EXAMPLE 50 Alkylation of Dichlorofluorene onto Xylene

Ferric chloride (0.03 g, 0.2 mmole) is weighed into a 50 mL 3-neckedflask fitted with a stirbar, nitrogen inlet, thermometer, and condenserwith drying tube. A mixture of dichlorofluorene (4.7 g, 20 mmol) ino-xylene (anhydrous, 20 mL) is added by syringe. The addition isexothermic at the beginning, raising the temperature from 25° to 30° C.The reaction is heated by means of a heating mantle to a temperature of40°-50° C. while a continuous stream of nitrogen is bubbled through themixture. The solution rapidly exhibits a dark red color, and begins toevolve HCl. The mixture is analyzed by the procedure of Example 15 onehour after addition is complete and shows formation of a single productappearing as a single peak at 13.58 minutes. This material is worked upby diluting with methylene chloride, washing the resulting solution withwater and 1M HCl, and then evaporating the solvent. The resulting tackysemisolid is then boiled in ethanol (100 mL) to precipitate a paleyellow solid. This solid is flushed through alumina with methylenechloride (100 mL), and the methylene chloride is quickly evaporated,leaving the product as a pale yellow semicrystalline solid, yield 7.47g, 99.7 percent of theoretical. Analysis of the product by GC/MS showed98.3 percent of the product as a single peak with 1.7 percent of theproduct as an isomer. The spectral peaks are: GC/MS: 375 (29.76); 374(100.00); 360 (18.1); 359 (37.14); 269 (10.75); H-NMR: delta 2-2.5(12H), 6.8-7.9 (14H).

EXAMPLE 51 Alkylation of Aniline

The procedure of example 39 is repeated except that aniline is used asthe aromatic compound to produce 9,9-bis(4-aminophenyl)fluorene(abbreviated BAPF) in the number of equivalents indicated. Byproductssuch as 9-(2-aminophenyl)-9-(4-aminophenyl)fluorene and N,p-BAPF arerearranged to p,p-BAPF. Formation of BAPF is followed by gaschromatography on a 15 m capillary column. Results shown in Table 5indicate isomerization of byproducts to p,p-BAPF.

                  TABLE 5                                                         ______________________________________                                        BAPF PREPARATION                                                                         Selectivity (%)                                                    Temp. React. Time                  o,p-  N,p-                                 (°C.)                                                                        (min)      p,p-BAPF  Monoamine                                                                             BAPF  BAPF                                 ______________________________________                                        135   30         60.05     17.55   1.37  19.97                                135   60         81.57     2.80    1.41  14.20                                135   90         81.56     2.70    2.30  13.43                                135   120        87.32     1.75    1.49  7.42                                 135   150        93.23     0       2.17  4.59                                 135   210        95.57     0       1.89  2.53                                 135   300        95.71     0       2.32  1.96                                 135   390        96.38     0       1.89  1.72                                 ______________________________________                                         The data in this table shows that over the indicated periods of time,         product is formed and byproducts rearrange to the desired p,pisomers.    

The data in this table shows that over the indicated periods of time,product is formed and by products rearrange to the desired p,p-isomers.

EXAMPLE 52 Alkylation of Dichlorofluorene onto Benzocyclobutane

DCF (19.14 g, 0.0814 mole) and benzocyclobutane (69.12 g, 0,664 mole)are weighed into a dry 100 mL 14/20 flask and stirred under nitrogenuntil most of the DCF has dissolved. Antimony pentachloride (5 mL, 0.005mole) is transferred by syringe into an oven-dried 250 mL three-neckedflask fitted with a nitrogen inlet, stirbar, condenser, thermometer, anddrying tube. Dry dichloromethane (65 mL) is added to the reaction flaskand an additional 20 mL of dry dichloromethane is added to the DCF/BCBsolution (for complete dissolution of the DCF). The catalyst solution inthe reaction flask is stirred and purged with a stream of nitrogen asthe DCF/BCB solution is added by syringe. The mixture turns burgundyimmediately and gives off HCl. The reaction is warmed as necessary tomaintain a temperature of about 40° C. An additional 15 mL ofdichloromethane is used to rinse in the last of the DCF/BCB mixture intothe reaction. After addition is complete, the mixture is heated at 40°C. for an additional 2 hours and then allowed to stir overnight.

GC analysis of the product shows no residual DCF. The dichloromethanesolution is washed with water (with a color change to muddy yellowobserved) and 0.5 molar HCl. The solution is dried over MgSO₄, and thenconcentrated by rotary evaporation to yield a thick brown glass whichfoams as the last of the solvent and residual BCB is removed forming abrittle gold foam which can be easily crushed.

The resulting gold colored powder is analyzed by LC and shows theexpected mixture of bis-BCB adduct and BCB-fluorene oligomers along witha small amount of fluorenone. The product is fairly soluble in acetone.Addition of the acetone solution to ethanol causes formation of alight-colored precipitate. However, as the solution is heated to removethe acetone, and the temperature of the solution approaches 60°-80° C.,the product becomes tacky and the light-colored precipitate which hasbeen suspended in the boiling mixture clumps together into a dark goldmass.

As the solution cools, a light-colored "crystalline" materialprecipitates. The ethanol is decanted from the precipitated productwhich is weighed and analyzed by LC. Only half of the theoretical amountof product is found in this portion, and LC analysis shows that a majorportion of the bis-BCB adduct has been removed. The rest of the product(also containing an undetermined but significant amount of the bisadduct) has remained in the ethanol solution and is recovered by rotaryevaporation.

The product is dissolved in wet tetrahydrofuran and treated with 0.1 gof sodium borohydride to convert residual fluorenone to alcohol. After30 minutes of stirring, acetone is added, and the mixture is stirred for30 minutes to destroy excess sodium borohydride. The solvent is removedby rotary evaporation, and the product is dissolved in carbontetrachloride and treated with decolorizing carbon. The solution isflushed through neutral alumina to remove the fluorene alcohol and ioniccompounds. The solvent is then removed by rotary evaporation to producea light tan foam which is crushed. The material is analyzed by DSC, andthe melting point of the material is found to be very broad, withinitial softening occurring at about 50° C. and the material becomingdefinitely liquid by 100° C. NMR analysis (proton and carbon) shows verylittle ring damage.

Analysis of the powder by LC (liquid chromatography) shows it to be amixture of 9,9-bis(benzocyclobutanyl)fluorene (about 58 percent), a 3:2adduct,9-benzocyclobutanyl-9-((9-benzocyclobutanylfluoren-9-yl)benzocyclobutanyl)fluorene(about 27 percent) and 15 percent higher oligomers. Proton NMR showsbroad overlapping singlets at delta 3-3.2 from TMS (tetramethylsilane)(CH₂ 's of the cyclobutane rings) and a complex pattern of multiplets atdelta 7-7.9 (aromatic protons) in a ratio of 1:2, aliphatic to aromatic.Carbon NMR shows three signals for aliphatic CH₂ at 29.35, 29.53, and29.81 ppm (relative to TMS) and three signals for quaternary aliphaticcarbons at 66.16, 66.33, and 66.40 ppm. The material is cured at 160° C.for one hour and 210° C. for 12 hours. The resulting amber-coloredplaque shows a 2 percent loss in weight when heated to 400° C.

A small portion of the product (1.5 g) is placed in an aluminum weighingdish and degassed and melted under vacuum up to 115° C. The material iscured at 160° C. for 1 hour and then cured at 210° C. for 12 hours. Aclear amber-colored plaque is obtained which is somewhat brittle. Theresulting amber-colored plaque shows a 2 percent loss in weight whenheated to 400° C.

EXAMPLE 53 Alkylation of Dichlorofluorene onto p-Cresol

Dichlorofluorene (23.66 g) is weighed into a 500 mL four-neckedround-bottomed flask equipped with a magnetic stir bar, heating mantle,thermometer, nitrogen inlet and drying tube. Molten p-cresol (114 g,about 40° C.) is added rapidly and the mixture immediately turns purpleand begins to vent HCl. The mixture is stirred for one hour under asweep of nitrogen. Analysis of the mixture by GC shows formation of asingle product. After stirring for an additional hour during which muchof the product precipitates, the excess p-cresol is removed by vacuumdistillation. The residue is recrystallized from carbon tetrachloride toyield 9,9-bis(2-hydroxy-5-methylphenyl)fluorene in greater than 95percent yield. H-NMR (relative to TMS) delta 1.93 (singlet, 6H, CH₃),6.41 (singlet, 2H), 6.59-6.74 (AB, 4H), 7.17-7.32 (multiplet, 4H),7.76-7.95 (multiplet, 4H), 8.81 (singlet, 2H, OH). C-NMR: (ppm) 151.76,150.56, 137.63, 129.18, 125.59, 125.40, 125.32, 124.54, 124.48, 117.99,113.83, 60.37 (quaternary carbon), 18.75 (CH₃). This bisphenol iscyclized to the spirocyclic ether,2',7'-dimethylspiro[9H-fluorene-9,9'-[9H]xanthene] by refluxing intoluene with catalytic amounts of triflic, toluenesulfonic, ormethanesulfonic acid, or by refluxing in acetonitrile/water. Thespirocyclic ether is easily separated from the starting bisphenol byslurrying mixtures of the two in a nonsolvent for the spiro-ether suchas acetonitrile followed by filtration. H-NMR delta 2.02 (singlet, 6H,CH₃), 6.16-6.17 (multiplet, 2H), 6.96-7.0 (multiplet, 2H), 7.0-7.4(multiplet, 8H), 7.80-7.84 (multiplet, 2H). C-NMR: (ppm) 154.99, 149.37,139.57, 132.24, 128.81, 128.28, 127.67, 127.60, 125.65, 124.35, 119.8,116.33, 54.22 (quaternary carbon), 20.56 (CH₃).

EXAMPLE 54 Alkylation of Dichlorofluorene onto Resorcinol

Dichlorofluorene (23.51 g) is added to a solution of resorcinol (110.11g) in 500 mL of dry acetonitrile with stirring. The mixture is held atabout 40° C. and swept with nitrogen for 4 hours. Analysis of thereaction mixture by LC shows formation of the bisphenol9,9-bis(2,4-dihydroxyphenyl)fluorene as the major product (about 60percent) with the balance as the spirocyclized bisphenol etherspiro[fluorene-9,9'-xanthene]-3',6'-diol (about 25 percent) and higheroligomers. The excess resorcinol is removed by vacuum distillation.

Recrystallization of the residue from acetonitrile affords a purifiedsample of the bisphenol. H-NMR (relative to TMS) (in DMSO): delta5.88-6.40 (m, 6H), 7.15-7.30 (m, 4H), 7.75-7.78 (m, 4H), 8.84 (s, 2H,OH), 8.93 (s, 2H, OH). C-NMR (ppm): 158.8, 156.77, 153.55, 139.63,127.37, 126.94, 126.40, 119.97, 106.56, 105.36, 103.56, 61.44(quaternary carbon). The crude mixture is converted to the spirocyclicbisphenol ether, spiro[fluorene-9,9'-xanthene]-3',6'-diol by treatmentwith acid or refluxing in toluene with acid catalyst as in Example 52.H-NMR (DMSO): delta 6.3-6.9 (m, 5H), 7.3-8.2 (multiplet, 8H), 9.8(singlet, 2H).

EXAMPLE 55 Alkylation of Dichlorofluorene onto Hydroquinone

The reaction is carried out using the same procedure as in Example 54,substituting hydroquinone for resorcinol. The spirocyclic bisphenolether, spiro[fluorene-9,9'-xanthene]-2',7'-diol is isolated as anoff-white powder. H-NMR (DMSO): delta 5.9-6.95 (multiplet, 4H),7.38-8.25 (multiplet, 1 OH), 9.2 5 (singlet, 2H)

EXAMPLE 56 Alkylation of Dichlorofluorene onto a Mixture ofBenzocyclobutane and Phenyl Ether.

The reaction is carried out using the same procedure as Example 52,substituting a solution of dichlorofluorene, benzocyclobutane and phenylether (2:6:1 molar ratio) in dichloromethane for the solution ofdichlorofluorene and benzocyclobutane. The reaction mixture is flushedthrough neutral alumina to remove antimony salts and the product isisolated from the solution by rotary evaporation. The resulting brittleorange foam is crushed to a powder, dissolved in dichloromethane andtreated with decolorizing carbon. Evaporation of the solvent yields ayellow powder. H-NMR:delta 2.95-3.2 (broad overlapping singlets, CH₂'s), 6.82-8.0 (multiplet, aromatic H) in a ratio of 1:5.

EXAMPLE 57 Preparation ofSpiro[9H-fluorene-9,9'-[9H]xanthene]-2',7'-dicarboxylic acid; Oxidationof 2',7'-Dimethylspiro[9H-fluorene-9,9'-[9H]xanthene]

Cobalt acetate dihydrate (0.25 g),2',7'-dimethylspiro[9H-fluorene-9,9'-[9H]xanthene] (1.8 g),o-dichlorobenzene (10 mL), and acetic acid (8 mL) are transferred into a25 mL three-necked round-bottomed flask equipped with a magneticstirbar, condenser, air inlet, and thermometer. Hydrobromic acid (30percent by weight in acetic acid, 0.2 mL) is added by syringe and themixture is stirred and heated to 120°-125° C. as a stream of air israpidly bubbled through the solution. The progress of the reaction isfollowed by LC analysis. Heating and aeration of the reaction arecontinued for 48 hours. The reaction mixture is then cooled and washedwith water to remove the acetic acid. The organic layer is extractedwith aqueous sodium hydroxide (1M) to remove the product acid as itssodium salt. Acidification of the base layer with concentrated HClcauses precipitation of the product,spiro[fluorene-9,9'-xanthene]-2',7'-dicarboxylic acid, as a yellowishpowder, which is filtered off, washed with water and dried. H-NMR(DMSO): delta 6.88-6.89 (m, 2H), 7.05-7.11 (m, 2H), 7.19-7.24 (m, 2H),7.35-7.45 (m, 4H), 7.80-7.84 (m, 2H), 7.96-8.03 (m, 2H), 10.55 (bs, 2H).C-13 NMR (DMSO), (ppm): 166.09 (acid C═O), 154.19, 153.35, 139.02,129.95, 129.22, 128.92, 128.58, 126.51, 125.23, 124.29, 120.81, 117.34,53.14 (quaternary carbon) where m=multiplet, s=singlet and bs=broadsinglet.

EXAMPLE 58 Preparation of 9,9-Bis(3,4-diaminophenyl)fluorene; Alkylationof 9,9-Dichlorofluorene with o-Phenylene Diamine

Into a three-necked 100 mL round-bottomed flask is placed o-phenylenediamine (26 g). The flask is then equipped with a drying tube, magneticstirbar, thermometer, powder addition funnel, and nitrogen inlet. Theo-phenylene diamine is then stirred and heated to 105° C. and solid9,9-dichlorofluorene is added to the melt. An immediate reaction occursas evidenced by a color change to dark brown, formation of a copiousprecipitate and an increase in temperature to 110°-120° C. Thetemperature is then increased to 130° C. and held there for 4 hoursduring which time the mixture becomes more liquid. The reaction is thenallowed to cool and the excess o-phenylenediamine is removed by pouringthe reaction mixture into ethanol and filtering. The resulting darkbrown solid is recrystallized from toluene to yield9,9-bis(3,4-diaminophenyl)fluorene. H-NMR (DMSO): delta 4.97 (bs, 8H,NH₂), 6.07-6.11 (m, 2H), 6.31-6.42 (m, 4H), 7.17-7.33 (m, 6H), 7.76-7.79(m, 2H). C-13 NMR (DMSO) (ppm): 152.55, 139.71, 136.29, 134.37, 132.64,127.56, 127.17, 126.40, 120.37, 118.36, 117.69, 115.63, 115.11, 64.4(quaternary carbon) where s=singlet, m=multiplet, and bs=broad singlet.

Example 59 Preparation of 9,9-Bis(4-amino-3-ethylphenyl)fluorene.

The procedure of Example 39 is repeated except that 0.537 mole of2-ethylaniline is used in place of aniline and, after stirring at 60°C., the temperature is raised to 175° C.9,9-Bis(4-amino-3-ethylphenyl)fluorene (abbreviated EAPF), has amolecular weight of 404 (determined by mass spectroscopy) and a meltingpoint of 191°-192° C., and is prepared in 92 percent yield. Results areshown in Table 6.

Example 60 Alkylation of 2-Ethylaniline

The procedure of Example 59 is repeated. After the reaction temperatureis raised to 175° C., the formation of9,9-bis(4-amino-3-ethylphenyl)fluorene isomers (abbreviated BEAPF) isfollowed by gas chromatography on a 15 m capillary column. The resultsare shown in Table 6.

                  TABLE 6                                                         ______________________________________                                        BEAPF PREPARATION                                                             Temp. React. Time                                                                              Selectivity (%)                                              (°C.)                                                                        (hours)    p,p-BEAPF  Monoamine                                                                             N,p-BEAPF                                 ______________________________________                                        175   1          40.47      40.47   1.11                                      175   2          79.80      18.84   1.36                                      175   3          88.09      10.35   1.56                                      175   4          92.40      6.28    1.33                                      175   5          94.83      4.16    1.01                                      175   6          96.59      2.31    1.10                                      ______________________________________                                         *Formation of o,pisomer was not observed                                 

The data in this table shows that over the indicated periods of time,product is formed and byproducts rearrange to the desired p,p-isomers.

Example 61 Preparation of 9,9-Bis(N-methyl-4-aminophenyl)fluorene.

The procedure of Example 39 is repeated except that 0.537 mole ofN-methylaniline is used in place of the aniline and, after stirring at60° C., the temperature is raised to 135° C.9,9-Bis(N-methyl-4-aminophenyl)fluorene (abbreviated BNMAPF), has amolecular weight of 376 (as determined by mass spectroscopy) and amelting point of 203°-204° C., and is prepared in 85 percent yield.Results are shown in Table 7 in the next Example.

Example 62 Alkylation of N-methylaniline

The procedure of Example 59 is repeated using 0.537 mole ofN-methylaniline. After the reaction temperature is raised to 135° C.,the formation of 9,9-bis(N-methyl-4-aminophenyl)fluorene (abbreviatedBNMAPF) is followed by gas chromatography on a 15 m capillary column.The data in Table 7 shows that over the indicated periods of time,product is formed and byproducts such as o,p-BNMAPF rearrange to thedesired p,p-isomer.

                  TABLE 7                                                         ______________________________________                                        BNMAPF PREPARATION                                                                    Selectivity (%)                                                                                       Dealk-                                              React.                    ylated.                                       Temp. Time    p,p-              by-    o,p-                                   (°C.)                                                                        (min.)  BNMAPF    Monoamine                                                                             product                                                                              BNMAPF                                 ______________________________________                                        135   60      86.6      1.9     2.1    9.4                                    135   120     89.4      3.4     1.3    5.9                                    135   180     91.2      1.5     2.2    5.1                                    135   235     93.0      1.0     2.0    4.1                                    135   310     92.0      2.1     3.1    2.8                                    135   460     92.3      2.5     3.5    1.7                                    ______________________________________                                    

The data in this table shows that over the indicated periods of time,product is formed and byproducts rearrange to the desired p,p-isomers.

Example 63 Preparation of 9,9-Bis(4-amino-3-chlorophenyl)fluorene.

The procedure of Example 39 is repeated except that 0.537 mole of2-chloroaniline is used in place of the aniline and, after stirring at60° C., the temperature is raised to 175° C.9,9-Bis(4-amino-3-chlorophenyl)fluorene (abbreviated BACPF) has amolecular weight of 404 (as determined by mass spectroscopy) and amelting point of 235°-236° C., and is prepared in 94 percent yield.Results are shown in Table 8.

Example 64 Alkylation of 2-chloroaniline

The procedure of Example 63 is repeated. After the reaction temperatureis raised to 175° C., the formation of9,9-bis(4-amino-3-chlorophenyl)fluorene (abbreviated BACPF) is followedby gas chromatography on a 15 m capillary column. Results are shown inTable 8.

                  TABLE 8                                                         ______________________________________                                        BACPF PREPARATION                                                             React.     Selectivity (%)                                                    Temp. Time     p,p-             Fluorenone                                                                            N,p-                                  (°C.)                                                                        (hr.)    BACPF    Monoamine                                                                             Byproduct                                                                             BACPF                                 ______________________________________                                        175   1        26.54    50.41   23.06   0.00                                  175   2        42.20    36.19   21.61   0.00                                  175   3        68.51    17.48   10.45   3.56                                  175   4        87.95    3.28    4.88    3.89                                  175   6        93.96    1.29    1.29    3.46                                  175   7        93.08    1.40    1.98    3.54                                  ______________________________________                                    

The data in this table shows that over the indicated periods of time,product is formed and byproducts rearrange to the desired p,p-isomers.The data in these tables shows that over the indicated periods of time,product is formed and byproducts such as o,p-BNMAPF and N,p-BAPFrearrange to the desired p,p-isomers.

EXAMPLE 65 Alkylation of Dichlorofluorene with 3,4-Dimethylphenol(Xylenol) and subsequent Oxidation and Hydrolysis of Resulting Products

Dichlorofluorene (23.51 g, 0.10 mole) is weighed into a powder additionfunnel and dissolved in mL of dry dichloromethane. Crystalline xylenol(73.3 g, 0.6 mole) is weighed into a 250 mL three-necked round-bottomedflask which is equipped with a stirrer, heating mantle, nitrogen inlet,condenser, thermometer, and drying tube. Dry dichloromethane (80 mL) isadded and the mixture is heated to 400° C. with stirring. The solutionof dichlorofluorene in dichloromethane is added slowly to the mixture asthe temperature is maintained at about 400° C. The reaction is rapid asevidenced by copious production of HCl. The mixture becomes cloudyrapidly as a large quantity of white precipitate is formed. Afteraddition is complete the reaction is stirred for an additional half hourand then checked by gas chromatography. The reaction is complete, andthe only products observed are the bisphenol(9,9-bis(2-hydroxy-4,5-dimethylphenyl)fluorene) and the spirocyclicether (2',3',6',7'-tetramethylspiro[fluorene-9,9'-xanthene]) in a moleratio of 9:1. The mixture is slurried with acetonitrile, chilled andfiltered to yield 39.69 g of white powder. Taking into account theamount of spiro-ether, this represents a yield of 98.07 percent. Thisproduct (35.59 g) is slurried in toluene (150 mL) along with 0.5 mL ofmethanesulfonic acid. The mixture is refluxed with the water producedbeing trapped in a Dean-Stark trap. After 3 hours of heating thecyclization to form spiro-ether is complete. The homogeneous solution iswashed once with 50 mL of 0.5M aqueous NaOH to remove methanesulfonicacid catalyst, dried over magnesium sulfate, and concentrated to yieldthe product as a yellow solid. The solid is slurried in acetone andfiltered to give the spiro-ether(2',3',6',7'-tetramethylspiro[fluorene-9,9'-xanthene]) as a white solid(33.58 g, 98.7 percent yield).

9,9-bis(2-hydroxy-4,5-dimethylphenyl)fluorene

H-1 NMR: (DMSO) delta from tetramethylsilane 1.82 (singlet, CH₃, 3H),2.01 (singlet, CH₃, 3H), 6.32-6.46 (doublet, 4H), 7.17-7.33 (multiplet,4H ), 7.78-7.88 (multiplet, 4H), 8.69 (singlet, 2H, OH); C-13 NMR:(DMSO) (ppm) 18.8 (CH₃), 19.0 (CH₃), 61.5 (quaternary carbon), 117.2,119.8, 124.7, 126.2, 126.9, 127.3, 127.9, 128.2, 134.2, 139.3, 152.6,153.5. 2',3',6',7'-tetramethylspiro[fluorene-9,9'-xanthene] H-1NMR:(CDCl₃) delta from tetramethylsilane 1.87 (singlet, CH₃, 3H), 2.16(singlet, CH₃, 3H), 6.08 (singlet, 2H), 6.97 (singlet, 2H), 7.15-7.36(multiplet, 6H), 7.76-7.79 (doublet, 2H). C-13 NMR: (CDCl₃) (ppm) 18.9(CH₃), 19.4 (CH₃), 53.7 (quaternary carbon), 117.4, 119.8, 121.7, 125.6,127.5, 128.2, 128.3, 131.1 136.6, 139.6, 149.5, 155.5

Oxidation of 2',3',6',7'-Tetramethylspiro[fluorene-9.9'-xanthene] toform Spiro[fluorene-9.9-xanthene]-2',3',6',7'-tetracarboxylicdianhydride

Tetramethylspiro[fluorene-9,9'-xanthene] (7.77 g, 0.02 mole) is weighedinto a 500 mL three-necked flask along with cobalt acetate hydrate (0.5g, 0.002 mote), potassium bromide (0.24 g, 0.002 mole) and methyl ethylketone (0.5 g, 0.007 mole). Propionic acid (200 mL) is added and theflask is equipped with a condenser, gas sparge tube, magnetic stirbar,thermometer, and air outlet. The flask is lowered into a hot oil bathmaintained at a temperature of 140° C. and the mixture is heated andstirred as air is introduced under the surface of the solution at a rateof 1 cubic foot per hour (28.3 L/h or 472 mL/min). The reaction isfollowed by sampling at intervals and analyzing by LC. After 22 hours at125° C. (internal temperature) all of the starting material disappearsand several products are formed. The temperature of the oil bath isincreased to 145° C. and heating is continued for another 20 hours atthis point the product mixture consists of mixed acids, so 5 mL ofpropionic anhydride is added, and the mixture is heated for 12 hours.Analysis of the mixture by liquid chromatography shows the formation ofa single productspirol[fluorene-9,9'-xanthenel-2',3',6',7'-tetracarboxylic dianhydride.The mixture is concentrated by rotary evaporation and the residue isdissolved in dichloromethane and washed with cold water to removeinorganic salts. The dichloromethane solution of the product is thendried over 4A (Angstrom, 4×10⁻¹⁰ m) molecular sieves, filtered andconcentrated to yield the product as a light tan solid. H-1NMR: deltafrom tetramethysilane 7.88-7.95 (multiplet, 4H), 7.48-7.55 (multiplet,2H), 7.26-7.32 (multiplet, 2H), 7.0-7.11 (multiplet, 4H). C-13 NMR:(ppm) 54.5 (quaternary C), 114.8, 121.3, 125.2, 126.7, 126.9, 129.5,129.9, 132.1, 133.3, 139,5, 152.7, 155.6, 161.5 (C═O).

Hydrolysis of Spiro[fluorene-9.9'-xanthene]-2',3',6',7'-tetracarboxylicdianhydride to Spirolfluorene-9.9'-xanthene]-2',3',6',7'-tetracarboxylicacid

A sample of the dianhydride is warmed to 50° C. in 4 equivalents of 1Mcaustic (NaOH) solution. The solution is then acidified, withconcentrated hydrochloric acid and the tetracarboxylic acid is isolatedin quantitative yield by filtration from the solution. The materialgives one peak by liquid chromatography. The proton and carbon spectraare taken of the salt form in D₂ O since the free acid is insoluble instandard NMR solvents. H-1NMR: delta from tetramethylsilane 6.97-7.08(multiplet, 7H), 7.16-7.23 (multiplet, 2H), 7.66-7.7 (multiplet, 3H).C-13 NMR: (ppm, D₂ O) 55.2 (quaternary C) 117.9, 123.4, 126.8, 128.3,130.4, 131.4, 131.6, 135.3, 142.4, 153.8, 157.2, 178.3 (C═O), 179.6(C═O).

EXAMPLE 66 Reaction of Dichlorofluorene with Benzocyclobutane and FerricChloride Catalyst

DCF (23.51 g, 0.1 mole) and benzocyclobutane (BCB) (21.93 g, 0.21 mole)are weighed into a dry 100 mL 14/20 flask and stirred under nitrogenuntil most of the DCF has dissolved. Ferric chloride (0.08 g, 0.0005mole) is weighed into an oven-dried 250 mL three-necked flask fittedwith a nitrogen inlet, stirbar, condenser, thermometer, and drying tube.Dry dichloromethane (50 mL) is added and the mixture is stirred as theDCF/BCB solution is added by syringe while a sweep of nitrogen gas ispassed over the mixture. The mixture turns purple immediately and givesoff HCl. The reaction is warmed as necessary to maintain a temperatureof about 40° C. An additional 50 mL of dichloromethane is used todissolve and rinse in the last of the DCF/BCB mixture.

After addition is complete, the mixture is heated at 40° C. for anadditional 2 hours and then allowed to stir overnight. GC (gaschromatographic) analysis of the product shows no residual DCF. Thedichloromethane solution is washed with water (a color change of purpleto muddy green-yellow is observed) and 0.5 molar HCl (hydrochloricacid). The solution is dried over MgSO₄, and then concentrated by rotaryevaporation to yield a thick brown glass.

The product is then dissolved in a minimum amount of dichloromethane andpoured with stirring into 300 mL of acetone. This causes theprecipitation of off-white solid which is collected and dried(weight=5.21 g, 41 percent of theoretical). The LC (liquidchromatograph) contains several peaks, the largest of which is at 21.47minutes [the expected position of the difunctional product(9,9-bis(benzocyclobutanyl)fluorene) is about 11.7 minutes by comparisonwith an LC of a sample of the material made from DCF and an excess ofBCB]. The yellow filtrant is then diluted with water, and precipitationof white solid is observed. The LC analysis of this material shows themain peak to be at 11.77 minutes, corresponding to the bis-adduct madeby the previous reaction. Addition of more water causes theprecipitation of more solid which is collected. As more water is added,the precipitate finally becomes sticky and difficult to filter. Thematerial is only slightly soluble in acetonitrile. Proton and C-13 NMR'swere run on the two fractions. These are very similar for the twomaterials. Interestingly, the C-13 of the first material shows only onesignal for the CH₂ 's of the cyclobutane ring, and the second material(acetone soluble) shows two signals for these carbons. DSC's (dynamicscanning calorimetry) are run of the two materials, as well. The scansshow an exotherm starting at 217° C., corresponding to the ring-openingand polymerization of the BCB groups.

EXAMPLE 67 Reaction of DCF with Benzocyclobutane (BCB) and Phenyl Ether(DPO) (2:3:1) Antimony Pentachloride Catalyst

DCF (20.22 g, 0.086 mole), phenyl ether (7.32 g, 0.043 mole) andbenzocyclobutane (27 g, 0.259 mole) are weighed into a dry 100 mL 14/20flask and stirred under nitrogen until most of the DCF has dissolved.Antimony pentachloride(3.5 mL, 0.00344 mole) is weighed into anoven-dried 250 mL three-necked flask fitted with a nitrogen inlet,stirbar, condenser, thermometer, and drying tube. Dry dichloromethane(65 mL) is added to the reaction flask and an additional 20 mL of drydichloromethane is added to the DCF/DPO(diphenyl oxide)/BCB solution(for complete dissolution of the DCF). The catalyst solution in thereaction flask is stirred and purged with a stream of nitrogen as theDCF/DPO/BCB solution is added by syringe over a period of 3 hours. Themixture turns purple immediately and gives off HCl.

The reaction is warmed as necessary to maintain a temperature of about40° C. An additional 15 mL of dichloromethane is used to rinse in thelast of the DCF/BCB mixture into the reaction. After addition iscomplete, the mixture is heated at 40° C. for an additional 2 hours andthen allowed to stir overnight. GC analysis of the product shows noresidual DCF. The dichloromethane solution is flushed through neutralalumina to remove residual antimony material. The solution is thenconcentrated by rotary evaporation to yield a thick orange glass whichfoams as the last of the solvent and residual BCB is removed forming abrittle gold foam which is easily crushed.

The resulting gold colored powder is analyzed by LC and shows theexpected mixture of bis-BCB/DPO adduct and BCB-DPO-fluorene oligomersalong with a small amount of fluorenone. The product is dissolved in wettetrahydrofuran and treated with 0.1 g of sodium borohydride to convertresidual fluorenone to alcohol. After 30 minutes of stirring, acetone isadded, and the mixture is stirred for 30 minutes to destroy excesssodium borohydride. The solvent is removed by rotary evaporation and theproduct is dissolved in dichloromethane (dark orange solution) andtreated with decolorizing carbon. The solution is flushed throughneutral alumina to remove the fluorene alcohol and ionic compounds. Thesolvent is then removed by rotary evaporation to produce a yellow foamwhich is crushed. The material is analyzed by DSC, and the melting pointof the material is found to be very broad, with initial softeningoccurring at about 80° C. and the material becoming definitely liquid by120° C. NMR analysis (proton and carbon) shows no significant ringdamage. A small portion of the product (2.0 g) is placed in an aluminumweighing dish and degassed and melted under vacuum up to 115° C. Thematerial is cured at 160° C. for 1 hour and then cured at 235° C. for 12hours. An orange plaque is obtained which can be removed intact.

EXAMPLE 68 Conversion ofSpiro[fluorene-9,9'-xanthene]-2',7'-dicarboxylic acid toSpiro[fluorene-9,9'-xanthene]-2',7'-dicarbonyl chloride

Spiro[fluorene-9,9'-xanthene]-2',7'-dicarboxylic acid prepared inExample 57 (1.25 g, 3 mmole) is stirred and heated to reflux in 15 mL ofoxalyl chloride until the solution clears. The excess oxalyl chloride isremoved by rotary evaporation and the resulting solid is dissolved indichloromethane and filtered to remove any unreacted diacid. Thedichloromethane solution is concentrated by rotary evaporation to givethe diacid chloride [spiro[fluorene-9,9'-xanthene]-2',7'-dicarbonylchloride] as an off-white solid. Recovered yields are quantative.Spiro[9H-fluorene-9,9'-[9H]xanthene]-2',7'-dicarbonyl chloride: H-1NMR:(CDCl₃) delta 7.06-7.48 (multiplet, 10H), 7.82-8.05 (multiplet, 4H).C-13 NMR: (CDCl₃) (ppm) 166.8, 155.5, 153.5, 139.6, 132.3, 129.3, 129.0,128.9, 128.8, 128.7, 125.2, 120.8, 117.8, 53.4 (quaternary carbon).

EXAMPLE 69 Reaction of Dichlorofluorene with m-Cresol and cyclization ofthe Products to form 3',6'-Dimethylspiro[fluorene-9,9'-xanthene]

Dichlorofluorene (DCF) (35.27 g, 0.15 mole) is weighed into a powderaddition funnel and dissolved in 20 mL of dry dichloromethane. Liquidm-cresol (64.88 g, 0.6 mole) is weighed into a 250 mL three-neckedround-bottomed flask which is equipped with a stirrer, heating mantle,nitrogen inlet, condenser, thermometer, and drying tube. Drydichloromethane (80 mL) is added and the mixture is heated to 40° C.with stirring. DCF solution is added slowly to the mixture as thetemperature is maintained at about 40° C. The reaction is rapid asevidenced by copious production of HCl bubbles after each addition.After addition is complete, the reaction is stirred for an additionalhalf hour and then checked by LC. The reaction is complete, and thechromatograph shows peaks for the desired bisphenol(9,9-bis(2-hydroxy-4-methylphenyl)fluorene) along with isomers. Themixture is dissolved in toluene and refluxed with 0.5 mL of methanesulfonic acid collecting water formed during the cyclization reaction ina Dean-Stark trap. The toluene is then removed by rotary evaporation andthe residue is slurried with acetonitrile, chilled and filtered to yieldthe spiroether [3',6'-dimethylspiro[fluorene-9,9'-xanthene] as anoff-white powder. The isomeric bisphenols formed in the alkylationreaction do not cyclize and remain dissolved in the acetonitrile.

Upon cooling the product,3',6'-dimethylspiro[9H-fluorene-9,9'-[9H]xanthene] (13.03 g)precipitates from the toluene solution as a white powder which isfiltered from the solution, and rinsed with toluene, sodium bicarbonatesolution and water. The toluene solution is washed with sodiumbicarbonate and 2M NaOH, dried over magnesium sulfate, and concentratedby rotary evaporation resulting in a brown oil. This oil is slurriedwith acetonitrile, chilled and filtered to yield 7.51 g of product as anoff-white powder. Isolated yield is 38 mole percent. H-1 NMR: (CDCl₃)delta 2.27 (singlet, CH₃, 6H), 6.25-6.28 (doublet, 2H), 6.54-6.58(doublet of doublets, 2H), 7.01-7.36 (multiplet, 8H), 7.75-7.78(multiplet, 2H). C-13 NMR: (CDCl₃) (ppm) 155.3, 151.2, 139.6, 138.1,128.3, 127.6, 125.6, 124.2, 121.7, 119.8, 117.0, 53.7 (quaternary carbon), 21.0 (CH₃).

EXAMPLE 70 Oxidation of 3',6'-Dimethylspiro[fluorene-9,9'-xanthene] toSpiro[fluorene-9,9'-xanthene]-3',6'-dicarboxylic acid

Dimethylspiro[fluorene-9,9'-xanthene] prepared as in Example 69 (10.00g, 0.0277 mol) is weighed into a 500 mL three-necked flask along withcobalt acetate hydrate (0.69 g, 0.00277 mol), sodium bromide (0.29 g,0.00277 mol) and methyl ethyl ketone (0.70 g, 0.0097 mol). Propionicacid (250 mL) is added and the flask is equipped with a condenser, gassparge tube, magnetic stirbar, thermometer, and air outlet. The flask islowered into a hot oil bath maintained at a temperature of 145° C. andthe mixture is heated and stirred as air is introduced under the surfaceof the solution at a rate of 1 cubic foot per hour (28.3 L/h or 472mL/min). The reaction is followed by sampling at intervals and analyzingby LC. After 36 hours at 135° C. (internal temperature) all of thestarting material disappears and a single product is seen by LC. Themixture is allowed to cool, whereupon a large quantity of whiteprecipitate forms and is filtered from the mixture and rinsed withpropionic acid and water. This material is insoluble in dichloromethane.The powder is dried in air. When reacted with sodium hydroxide in D₂ O,a gelatinous product forms. Spectra are consistent with the structure ofthe diacid, spirol[fluorene-9,9'-xanthene]-3',6'-dicarboxylic acid.Recovered yields are 85-95 mole percent.

EXAMPLE 71 Conversion ofSpirol[fluorene-9,9'-xanthene]-3',6'-dicarboxylic acid toSpirol[fluorene-9,9'-xanthene]-3',6'-dicarbonyl chloride

Spiro[fluorene-9,9'-xanthene]-3',6'-dicarboxylic acid prepared as inExample 70 (1.25 g, 3 mmole) is stirred and heated to reflux in 15 mL ofoxalyl chloride until the solution clears. The excess oxalyl chloride isremoved by rotary evaporation and the resulting solid is dissolved indichloromethane and filtered to remove any unreacted diacid. Thedichloromethane solution is concentrated by rotary evaporation to givethe diacid chloride [spiro[fluorene-9,9'-xanthene]-3',6'-dicarbonylchloride] as an off-white solid. Recovered yields are greater than 95mole percent.

EXAMPLE 72 Preparation of Spiro[9H-fluorene-9,9'-[9H]xanthene]

Dichlorofluorene (200.0 g, 0.85 mol) is mixed with aniline (1200 mL,13.17 mole) and heated slowly to 55°-60° C. and held there for 30minutes. GC analysis shows 4 mole percent of fluorenedianiline and 96mole percent 9-(4-aminophenyl)-9-chlorofluorene. The mixture is thenneutralized by washing with 1 L of 10 mole percent sodium hydroxide. Theorganic layer is separated and the excess aniline is removed by rotaryevaporation. The resulting product 9-(4-aminophenyl)-9-chlorofluorene istransferred to a 3 L flask along with phenol (1500 mL, 17 mole) andmethanesulfonic acid (300 mL). The mixture is heated to 170° C. for 7hours, then allowed to cool to room temperature overnight. The product,spiro[9H-fluorene-9,9'-[9H]xanthene] precipitates from the cooledmixture and is isolated by filtration. The precipitated crystals arewashed twice with sodium bicarbonate and twice with water to removeresidual methanesulfonic acid. Crude weight is 345 g, with GC analysisshowing 17 mole percent phenol remaining in the product. The product iswashed twice with 500 mL of methanol to remove phenol. Isolated yield is223 g (75 mole percent ). Spiro[9H-fluorene-9,9'-[9H]xanthene] GC/MS 332(100 percent), 302 (21.88 percent), 300 (18.75 percent), 255 (18.75percent), 200 (2.9 percent), 165 (14.61 percent).

What is claimed is:
 1. A compound selected from9,9-bis(4-ethylphenyl)fluorene, 9,9-bis(4-ethenylphenyl)fluorene,9,9-bis(4-ethynylphenyl)fluorene, 9,9-bis(2,3-dimethylphenyl)fluorene,9-(3,4-dimethylphenyl )9-(2,3-dimethylphenyl)fluorene,9,9-bis(3-amino-4hydroxyphenyl)fluorene,9,9-bis(4-amino-3hydroxyphenyl)fluorene, 9-(3-amino-4-hydroxyphenyl)-9(4-amino-3-hydroxyphenyl)fluorene,9,9-bis(1,3-isobenzofurandion-5-yl)fluorene,9,9-bis(benzocyclobutanyl)fluorene, 9,9-bis(4-halophenyl)fluorene,9,9-bis(dihydroxyphenyl)fluorene,spiro[9H-fluorene-9,9'-(9H)carbazine)-3',6'-diol,spiro(9H-fluorene-9,9'-(9H)carbazine)-3',6'-diamine,spiro(9H-fluorene-9,9'-(9H)carbazine)-2',7'-diamine,spiro(9H-fluorene-9,9'-(9H)xanthene)-2',7'-dicarboxylic acid,spiro(9H-fluorene-9,9'-(9H)xanthene)-3',6'-diamine,2',7'-diacetylspiro(9H-fluorene-9,9'-(9H)xanthene),spiro(9H-fluorene-9,13'-(13H)-6-oxapentacene)-2',10'-diolspiro(9H-fluorene-9, 13'-(13H)-6-oxapentacene)-3',9'-diol,3',6'diaminospiro(9H-fluorene-9,9'-thiaxanthene)-10',10'-dioxide,spiro(9H-fluorene-9,9'(9H, 10H)-dihydroanthracene-2',7'-bismaleimide,10-oxo-spiro(9H-fluorene-9,9'(9H, 10H)-dihydroanthracene)-3',6'-diamine,2',7'-dimethyl-spiro(9H-fluorene-9,9'-(9H)xanthene),2',7'-dicyano-spiro(9H-fluorene-9,9'-(9H)xanthene),2',7'-diformyl-spiro(9H-fluorene-9,9'-(9H)xanthene),2,7-diamino-3,6-dihydroxy-9,9'-spirobifluorene,2,7-diamino-3,6-dimethyl-9,9'-spirobifluorene,spiro(9H-fluorene-9,9'(9H,10H)-dihydroanthracene)-2',7'-diamine,2',3',6',7'-tetraaminospiro(9H-fluorene-9,9'-thiaxanthese)-10',10'-dioxide,spiro(9H-fluorene-9,9'(9H)xanthene)-2',3',6,7'-tetraamine,2,3,6,7-tetraamino-9,9'-spirobifluorene,2,7-diamino-9,9'-spirobifluorene-3,6-dithiol,2,7-bis(1-methyl-1-(4-hydroxyphenyl)-ethyl)spiro(xanthene-9,9'-fluorene),2,7-bis(4-hydroxyphenyl)spiro(xanthene-9,9'-fluorene),1,3,6,8,10,10-hexamethylspiro(dihydroanthracene-9,9'-fluorene)-2,7-diol,1,3,6,8-tetrabromo-10,10-dimethylspiro(dihydroanthracene-9,9'-fluorene)-2,7-diol,and 1,3,6,8-tetramethylspiro(dihydroanthracene-9,9'-fluorene)-2,7-diol,spiro(9H-fluorene-9,9'-(9H)xanthene)-3',6'-dicarboxylic acid,spiro(9H-fluorene-9,9'-(9H)xanthene)-2',7'-dicarbonyl chloride,spiro(9H-fluorene-9,9'-(9H)xanthene)-3',6'-dicarbonyl chloride,3',6'-dimethyl-spiro(9H-fluorene-9,9'-(9H)xanthene),2',7'-diisopropylspiro(9H-fluorene-9,9'-(9H)xanthene),3',6'-diisopropylspiro(9H-fluorene-9,9'-(9H)xanthene),2',3',6',7'-tetramethylspiro(9H-fluorene-9,9'-(9H)-xanthene),spiro(9H-fluorene-9,9'-(9H)xanthene)-2',3',6',7'-tetracarboxylic acid,or spiro(9H-fluorene9,9'-(9H)xanthene)-2',3',6',7'-tetracarboxylic aciddianydride, and mixtures thereof.
 2. A compound selected from9-(4-aminophenyl)-9-chlorofluorene,9-(4-(N-methylaminophenyl))-9-chlorofluorene,9-(4-amino-3-methylphenyl)-9-chlorofluorene,9-(4-amino-3-ethylphenyl)-9-chlorofluorene,9-(4-amino-3-chlorophenyl)-9-chlorofluorene,9-(4-amino-4-methylphenyl)-9-chlorofluorene,9-(4-amino-2-ethylphenyl)-9-chlorofluorene,9-(4-amino-2-chlorophenyl)-9-chlorofluorene, and mixtures thereof.
 3. Acompound of claim 1 selected from 9,9-bis(4-ethylphenyl)fluorene,9,9-bis(2,3-dimethylphenyl)fluorene, and 9-(3,4-dimethylphenyl)9-(2,3-dimethylphenyl) fluorene.
 4. A compound of claim 1 selected from9,9-bis(4-ethenylphenyl)fluorene, and 9,9-bis(4-ethynylphenyl)fluorene.5. A compound of claim 1 selected from9,9-bis(3-amino-4hydroxyphenyl)fluorene,9,9-bis(4-amino-3-hydroxyphenyl)fluorene,9-(3-amino-4-hydroxyphenyl)-9(4-amino-3-hydroxyphenyl)fluorene andmixtures thereof.
 6. A compound of claim 1 which is9,9bis(benzocyclobutanyl)fluorene.
 7. A compound of claim 1 selectedfrom 9,9-bis(4-halophenyl)fluorene.
 8. A compound of claim 1 selectedfrom 9,9-bis(dihydroxyphenyl)fluorene.
 9. A compound of claim 1 selectedfrom spiro(9H)fluorene-9,9'-(9H)xanthene)-2',7'-dicarboxylic acid,2',7'-dimethyl-spiro(9H-fluorene-9,9'-(9H)xanthene),spiro(9H-fluorene-9,9'-(9H)xanthane)-3',6'-dicarboxylic acid,spiro(9H-fluorene-9,9'(9H)xanthene)-2',7'-dicarbonyl chloride,spiro(9H-fluorene-9,9'-(9H)xanthene)-3',6'-dicarbonyl chloride,3',6'-dimethyl-spiro(9H-fluorene-9,9'-(9H)xanthene),2',3',6',7'-tetramethylspiro(9H-fluorene-9,9'-(9H)xanthene),spiro(9H-fluorene-9,9'-(9H)xanthene)-2',3',6',7'-tetracarboxylic acid,or spiro(9H-fluorene-9,9'-(9H)xanthene)-2',3',6',7'-tetracarboxylic aciddianydride, and mixtures thereof.
 10. A compound of claim 9 which isselected from spiro(9H-fluorene-9,9'-(9H)xanthene)-2',7'-dicarboxylicacid and mixtures thereof.
 11. A compound of claim 9 which is2,7-bis(4-hydrroxyphenyl)spiro(xanthene-9,9'-fluorene).
 12. A compoundof claim 9 which is selected fromspiro(9H-fluorene-9,9'-(9H)xanthene)-3',6'-dicarboxylic acid,spiro(9H-fluorene-9,9'-(9H)xanthene)-2',7'-dicarbonyl chloride,spiro(9H-fluorene-9,9'-(9H)xanthene)-3',6'-dicarbonyl chloride, andmixtures thereof.
 13. A compound of claim 9 which is selected fromspiro(9H-fluorene-9,9'-(9H)xanthene)-2',3',6',7'-tetracarboxylic acid,or spiro(9H-fluorene-9,9'-(9H)xanthene)-2',3',6',7'-tetracarboxylic aciddianydride, and mixtures thereof.